JP2003295431A - Photosensitive resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide-base photosensitive resin composition which utilizes a polyene-thiol crosslinking reaction through α,β-unsaturated bonds, suppresses reduction in film thickness in development and enables enhancement of resolution due to a small film thickness, prevention of corrosion of metal wiring and enhancement of adhesive power to metal wiring and to provide a method for producing the same. <P>SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor having a repeating unit of formula (1), (B) a polyfunctional polyene compound represented by the following formula, (C) a polyfunctional thiol compound represented by the following formula, (D) a dehydration condensing agent used in production of the polyimide precursor, (E) a photosensitive agent used for enhancing sensitivity to an actinic ray and (F) a solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide type photosensitive resin composition used as an electric / electronic insulating material in the production of semiconductor devices and the like and a method for producing the same. Thing
It is an insulating protective film formed on a semiconductor element such as an IC or an LSI, and is applied to a field in which fine pattern processing is required.

[0002]

2. Description of the Related Art In recent years, polyimide resins have been developed into electric and electronic fields including semiconductors due to their high heat resistance, chemical resistance, electric insulation, low dielectric constant, etc. , IC, LSI, VLSI are used as interlayer insulating films and surface protection films for chips. However, in the conventional polyimide film pattern forming method, after coating and drying the polyimide precursor on the wafer, it is necessary to perform pattern etching using a photoresist, which increases the cost. ,
In order to use a hydrazine solution, which is an environmentally harmful substance, as an etching solution, it is necessary to maintain the environment in which it is used and to strictly control the operation of waste treatment.

For this reason, material manufacturers have made attempts to introduce a photosensitive group into a polyimide precursor to enable pattern formation of the polyimide itself, and it has come to a practical stage in some product fields. However, the photosensitive polyimides currently in practical use can be roughly classified into those in which a photosensitive group is introduced into a polyimide precursor by an ionic bond and those in which a photosensitive group is introduced through an ester bond. The sensitivity to ultraviolet rays used in (1) is low (the difference in solubility is low), and the solubility of the resin decreases in the process, resulting in a low process margin. In the latter case, on the other hand, a complicated process is required in the production stage and a polymer having a molecular weight sufficient for practical use cannot be obtained.

Further, in recent years, the miniaturization of the IC process has been remarkably advanced, and the demand for improving the resolution of photosensitive polyimide has been increased, and at the same time, the use as an interlayer insulating film is required.
It is required to improve processing performance of photosensitive polyimide and introduce new process.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to utilize a polyene-thiol-based cross-linking reaction using an αβ unsaturated bond from a conventional cross-linking system using an ethylenic bond. This reduces film loss at the time of development due to oxygen inhibition during exposure, and since the same cured film thickness can be obtained, processing can be performed with a thinner thickness than in the past, so that resolution can be improved. Further, it is possible to prevent the corrosion of the metal wiring due to the acid block due to the esterification of the polyamic acid, and to improve the adhesion with the metal wiring by having the thiol bond. It is intended to provide such a polyimide precursor and a method for stably producing the polyimide precursor.

[0006]

Means for Solving the Problems As a result of intensive research aimed at achieving the above object, the present inventor has found that the above object can be achieved by adopting a resin composition described below and a method for producing the same. They have found and completed the present invention.

That is, the photosensitive resin composition of the present invention is
(A) a polyimide precursor having the following repeating units,

[Chemical 7] (In the formula, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO—, —SO. ₂ -, - CH ₂ - or -
A tetravalent organic group bonded by C (CF ₃ ) ₂
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
Is a divalent aromatic group bonded with-, R ³ and R ⁴ are
An organic group having an αβ unsaturated bond as well as being bonded via a hydroxyl group or —O— or —NH—,
And n is an integer of 1 or more) (B) Another functional polyene compound represented by the following general formula,

Embedded image wherein R ⁵ — (CH═CH ₂ ) _m (wherein R ⁵ is a single bond or —O—, —CO—, —CH ₂ —, An organic group bonded via SO ₂ — or —NH—, and m is 2 to
An integer of 4) (C) another functional thiol compound represented by the following general formula,

Embedded image R ⁶ — (CH ₂ —SH) _x (wherein, in R ⁶ , 1 to 3 thiol groups are single bonds or —O—, —CO—, —CH ₂ —, — It is an organic group bonded by SO ₂ — or —NH—, and x is an integer of 1 to 3) (D) A dehydration condensing agent used for producing the polyimide precursor, and (E) improved sensitivity to actinic rays. It is characterized in that it is composed of a photosensitizer used for the purpose and (F) a solvent.

Further, the method for producing the photosensitive resin composition of the present invention comprises (1) the acid dianhydride having the R ¹ skeleton shown in the repeating unit of the chemical formula 7 and the αβ unsaturated bond of R ³ and R ^4. In the esterification reaction step with a compound having a skeleton, (2) under the addition of a dehydration condensation agent, the esterification reaction product of (1) and R in Chemical formula 7
² polycondensation reaction step with a diamine compound to be a skeleton,
(3) a step of purifying the polycondensation-reacted polyimide precursor, and (4) the polyfunctional polyene compound represented by Chemical formula 8,
The method is characterized by including a step of preparing a polyimide precursor solution containing a polyfunctional polyene compound represented by and a photosensitizer used for improving sensitivity to actinic rays.

The present invention will be described in detail below.

First, the method for producing the photosensitive resin composition of the present invention will be described in the order of steps (1) to (4), and at the same time, the components (A) to (D) of the photosensitive resin composition of the present invention will be described. explain.

(1) Esterification reaction step between the acid dianhydride having the R ¹ skeleton in the formula of Chemical formula 7 and the compound having the αβ unsaturated bond of R ³ and R ^{4 in} the skeleton of the polyimide precursor of the present invention. Examples of the acid component having the R ¹ skeleton include pyromellitic acid, 3,3 ′, 4,
4'-biphenyltetracarboxylic acid, 2,3,3 ',
4'-biphenyltetracarboxylic acid, 3,3 ', 4,
4'-benzophenone tetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2, 3,
6,7-naphthalene tetracarboxylic acid, 1,2,5,6
-Naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-butane tetracarboxylic acid, 1,2,4 , 5-Cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3 , 4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid and the like and their anhydrides can be used, and these can be used alone or in combination.

Examples of the compound having R ³ and R ⁴ skeletons which are introduced into the acid component serving as the R ¹ skeleton through an ester bond include allyl alcohol, allyl carbinol, 2- (allyloxy) -ethanol, glycerol-αα '. -Diallyl ether and the like can be mentioned, and these can be used alone or in combination. Moreover, these are 1.5-3.0 times mol with respect to the said acid component, Preferably they are 2.0-.
It can be used in a 2.5-fold molar range.

The esterification reaction of the acid component having the R ¹ skeleton with the compound having the R ³ and R ⁴ skeletons can be carried out, for example, by using an acid dianhydride having the R ¹ skeleton and an alcoholic compound having the R ³ and R ⁴ skeletons. As the reaction solvent, a polar aprotic solvent good for polyimide precursor synthesis, such as N-methyl-2-pyrrolidone, is used, and a basic catalyst for smoothly carrying out the reaction,
For example, it is preferably carried out at room temperature in the presence of triethylamine, pyridine, triethanolamine and the like. This basic catalyst can be used in a range of 1.5 to 3.0 times, preferably 2.0 to 2.5 times the mol of the above acid component.

(2) With the addition of the dehydration condensing agent, the above-mentioned
Stell compound and R in the above formula ²Zia with a skeleton
Polycondensation reaction process with min compounds R used in the present invention²As a diamine compound with a skeleton
Is, for example, m-phenylenediamine, p-phenylene
Diamine, 2,4-diaminotoluene, 2,5-diami
Notourin, 2,6-diaminotoluene, 3,5-dia
Minotoluene, 1-methoxy-2,4-diaminobenze
1,4-diamino-2-methoxy-5-methylben
Zen, 1,3-diamino-4,6-dimethylbenzene,
1,2-diaminonaphthalene, 1,4-diaminonaphthalene
Ren, 1,5-diaminonaphthalene, 1,6-diamino
Naphthalene, 1,7-diaminonaphthalene, 1,8-di
Aminonaphthalene, 2,3-diaminonaphthalene, 2,
6-diaminonaphthalene, 1,4-diamino-2-methyi
Lunaphthalene, 1,5-diamino-2-methylnaphthalene
1,3-diamino-2-phenylnaphthalene, 2,
2-bis (4-aminophenyl) propane, 1,1-bi
Su (4-aminophenyl) ethane, 4,4'-diamino
Diphenylmethane, 3,3'-dimethyl-4,4'-di
Aminodiphenylmethane, 3,3 ', 5,5'-tetra
Methyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-5,5'-diethyl-4,4'-dia
Minodiphenylmethane, 3,3 ', 5,5'-tetrae
Cyl-4,4'-diaminodiphenylmethane, 4,4 '
-Methylenebis (cyclohexylamine), 4,4'-
Methylenebis (3,3-dimethyl-cyclohexylamido
), 2,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfide, 3,3'-dia
Minodiphenyl sulfone, 4,4'-diaminodiphe
Nilsulphone, 4,4'-diaminobenzanilide,
3,3'-diaminodiphenyl ether, 3,4'-di
Amino diphenyl ether, 4,4'-diamino diphe
Nyl ether, bis (4-aminophenyl) diethyl
Orchid, bis (4-aminophenyl) diphenylsilane,
Bis (4-aminophenyl) -N-methylamine, bis
(4-aminophenyl) -N-phenylamine, 3,
3'-diaminobenzophenone, 4,4'-diaminobenzoate
Nzophenone, 2,6-diaminopyridine, 3,5-di
Aminopyridine, 4,4'-diaminobiphenyl, 3,
3'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dihydroxy
Ci-4,4'-diaminobiphenyl, o-toluidine
Rufon, 4,4'-bis (4-aminophenoxy) bi
Phenyl, 2,2-bis [4- (4-aminophenoxy
Si) phenyl] propane, bis [4- (4-aminophen)
Noxy) phenyl] ether, bis [4- (4-amino)
Phenoxy) phenyl] sulfone, bis [4- (3-
Aminophenoxy) phenyl] sulfone, 1,4-bi
Su (4-aminophenoxy) benzene, 1,3-bis
(4-Aminophenoxy) benzene, 9,10-bis
(4-Aminophenyl) anthracene, 9,9-bis
(4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenyl) hexafluoropropane, 2,2-
Bis (3-aminophenyl) hexafluoropropane,
1,1-bis (4-aminophenyl) -1-phenyl-
2,2,2-trifluoroethane, 2,2-bis (3-
Amino-4-hydroxyphenyl) hexafluoropro
Bread, 2,2-bis (3-amino-4-methylpheny
Le) hexafluoropropane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropa
These can be used alone or in combination of two or more.
Can be used. In addition, these compounds are R¹Skeleton
0.5 to 2 times the molar amount of acid dianhydride
Is preferred, but it should be adjusted according to the purpose of use, final viscosity,
Can be used in the range of 0.8 to 1.2 times mol
It

Here, the (D) dehydration condensing agent used in the above polycondensation reaction in the present invention will be described.

When the above ester compound and the diamine component are reacted by a polycondensation method, it is usually carried out using an acid chloride, but in the electric and electronic fields including semiconductor devices, the released chlorine ion is product reliability. In the case of carrying out the polymerization by the acid chloride method, it is necessary to sufficiently wash with pure water after polycondensation because it causes a defect. As another polycondensation method, DCC which is a dehydration condensation agent
Although it is possible to use a carbodiimide derivative such as (dicyclohexylcarbodiimide), there are problems such as side reactions occurring simultaneously, gelation of the polyimide precursor, toxicity, and the complete removal of urea generated as a by-product. Have difficulty. Therefore, the reaction system must be cooled, the dehydration condensing agent must be added in several batches, or the molar balance between the acid component and the diamine component must be disrupted before use. In addition, as another method, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate and its derivative, diphenyl (2,3 -Dihydro-2-thioxo-3-benzothiazole) phosphonate and a derivative thereof, a polycondensation method can be mentioned. In this method, stable production is possible under mild conditions.
It is possible to obtain a polyimide precursor having high resolution and high film properties. These may be used alone or in combination of two or more. These may be added in an amount of 1 to 4 times, preferably 2 to 3 times the mol of the above ester compound.

As the solvent for the polycondensation reaction of the polyimide precursor used in the present invention, for example, N-methylpyrrolidone,
An aprotic polar solvent such as N, N'-dimethylacetamide or N, N'-dimethylformamide, cyclohexanone, cyclopentanone, γ-butyrolactone or the like is used, and these are used alone or in combination of two or more. be able to.

(3) Step of Purifying Polycondensation Precursor of Polyimide Precursor The solution obtained in the above step is re-charged by adding a poor solvent such as methanol, ethanol, isopropyl alcohol, or water to a solution of a single solvent or a mixture of two or more solvents. Precipitated and filtered, and the filtered slurry is poured into a solution of a poor solvent such as methanol, ethanol, isopropyl alcohol, and water alone or in a mixture of two or more kinds, and the mixture is stirred, washed, and then precipitated. Is dried under reduced pressure to obtain the compound having the resin skeleton represented by the above chemical formula 7.

(4) The compound of the chemical formula 8 and the compound of the chemical formula 9
In the present invention, a polyfunctional polyene compound, a polyfunctional thiol compound, a photoreaction initiator and a sensitizer shown in Chemical formula 8 for the purpose of improving sensitivity and resolution are further prepared in the present invention. A sensitizer such as is added to a solvent and dissolved. A storage stabilizer or the like may be added as an optional component.

The polyfunctional polyene compound as shown in Chemical formula 8 is diallyl phthalate, isocyanuric acid diallyl ester, maleic acid diallyl ester, diallyl malonic acid diethyl ester, isophthalic acid diallyl ester, phthalic acid diallyl ester, Isocyanuric acid triallyl ester, isocyanuric acid diallyl-n-propyl ester, pyrocarbonic acid diallyl ester, diallyl sulfide, terephthalic acid diallyl ester, trimesic acid triallyl ester, citric acid triallyl ester, triallyl isocyanurate, Triallyl phosphate and the like can be mentioned, and these can be used alone or in combination of two or more kinds. The addition amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the composition.

The polyfunctional thiol compound as shown in Chemical formula 9 is 1,4-butanedithiol, 1,10-decanedithiol, 3,6-dioxa-1,8-octanedithiol, bis (2-mercaptoethyl). )ether,
1,4-bis (mercaptomethyl) benzene, 4,5-
Bis (mercaptomethyl) -o-xylene, 1,6-hexanedithiol, 1,3-propanedithiol, 1,
2-propanedithiol, 2,3-dimercapto-1-
Propanol, s-triazine-2,4,6-trithiol and the like can be mentioned, and these can be used alone or in admixture of two or more. The amount of addition is 10
0.1 to 10 parts by weight is preferable with respect to 0 parts by weight.

Examples of the photoreaction initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, 2,2'-diethoxyacetophenone and 2-hydroxy-2. -Acetophenone derivatives such as methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-
Isopropyl thioxanthone, diethyl thioxanthone, benzyl, benzyl dimethyl ketal, benzoin, benzoin methyl ether, 2,6'-di (4'-
Diazidobenzal) -4-ethylcyclohexanone,
Azide compounds such as 2,6′-di (4′-diazidobenzal) -4-butylcyclohexanone and 2,6′-di (4′-diazidobenzal) -4- (t-butyl) cyclohexanone, 1-phenyl-1, 2-butadion-2-
(O-Methoxycarbonyl) oxime, 1-phenyl-
Propanedion-2- (o-methoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-Ethoxycarbonyl) oxime, 1-phenyl-
Oximes such as 3-ethoxy-propanetrione-2- (o-benzoyl) oxime, N-phenylglycine,
Examples thereof include glycine derivatives such as N- (p-ethyl) phenylglycine and N- (p-methyl) phenylglycine, and these may be used alone or in combination of two or more. The addition amount of these is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition.

The photoreaction initiator used in the present invention is an i ray (365 nm) or g ray (436n) in ultraviolet rays.
The compound is not limited to the above compounds as long as it can efficiently generate a reactive radical in m).

As the sensitizer used in the present invention, for example, Michler's ketone, 4,4'-bis (diethylaminobenzophenone), 2,5-bis (diethylaminobenzal) cyclopentanone, 2,6-bis ( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4, 4'-bis (diethylamino) chalcone, 4,4'-bis (dimethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene)- Benzothiazole, 2- (p-dimethylaminophenylvinylene)- Nzochiazoru, 1,3-bis (4'-dimethylamino benzal) acetone, 3,3 '
-Carbonyl-bis (7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethanolamine, N-phenylethanolamine, NP-tolyldiethanolamine, N-phenylmethanolamine, 4 -Morphoninobenzophenone dimethylaminoisoamyl benzoate,
2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
1-Phenyl-5-mercapto-1H-tetrazole and the like can be mentioned, and these can be used alone or in combination of two or more kinds. The amount of addition is 100
0.1 to 10 parts by weight is preferable with respect to parts by weight. Also,
By using these sensitizers according to the wavelength to be used and further according to the required sensitivity, the resolution at each wavelength can be improved.

As the polymerization inhibitor for improving the storage stability of the resin, for example, hydroquinone derivatives such as hydroquinone, methylhydroquinone and butylquinone can be used. These compounds can be used alone or in combination of two or more. The addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.

The resin composition obtained according to the present invention is used in a state of being dissolved in a solvent. Examples of the solvent used for the dissolution include N-methylpyrrolidone,
Aprotic polar solvents such as N, N'-dimethylacetamide, N, N'-dimethylformamide, cyclohexanone, cyclopentanone, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Examples thereof include butyl lactate and γ-butyrolactone, which can be used alone or in combination of two or more.

Next, a method of using the resin composition of the present invention will be described.

When considering application to a semiconductor device, first, the resin composition is coated on a target wafer using a spin coater, and then the coating film is dried at 80 to 120 ° C. A mask having a pattern drawn on the obtained coating film is transmitted to irradiate active ultraviolet rays of 365 nm and 436 nm. Next, heat treatment is performed again at 80 to 120 ° C., and subsequently, an organic solvent such as N-methylpyrrolidone, N, N′-dimethylacetamide,
An aprotic polar solvent such as N, N'-dimethylformamide or a solution of cyclohexanone, cyclopentanone, γ-butyrolactone or the like alone or in a mixture of two or more is used to dissolve and develop only a portion not irradiated with active light rays, It is rinsed with a solution of methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate or the like, and spin dried.
As a developing method, a method such as spraying, paddle, dipping, and ultrasonic wave can be considered. As a result, a desired negative pattern can be obtained on the target wafer.
Further, by heat-treating this coating film, this resin composition can be imidized to form a polyimide film having excellent film characteristics.

[0029]

In other words, the greatest feature of the present invention is that the following negative pattern formation mechanism is discovered. The present resin composition, in the above-mentioned method of use, is subjected to a spin coating drying step on a substrate, and then a radical generator is reacted in an active ray irradiation part by irradiating this coating film with an active ray such as an ultraviolet ray, Radicals are generated. The generated radical guides the polyfunctional thiol group as shown in Chemical formula 9 to the radical, and the unsaturated bond of R ³ and R ^{4 in} Chemical formula 7,
Unsaturated bonds chemically react with each other to form a crosslinked structure.
As a result, only the portion irradiated with an actinic ray such as ultraviolet rays becomes insoluble and does not dissolve, and the unirradiated portion exhibits solubility in an organic solvent. Due to this high contrast, the photosensitive resin composition of the present invention can form a negative pattern having high resolution and good dimensional controllability.

Further, since R ³ and R ^{4 in} Chemical formula 7 protect the acid portion of the polyamide precursor, it is possible to prevent the metal wiring on the base material from being deteriorated by the heat treatment during imidization. became.

Furthermore, since the polyfunctional thiol compound shown in Chemical formula 9 is contained in the resin composition, it is possible to improve the adhesion to the metal wiring on the base material.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples.

Example 1 First, 1.0 mol of benzophenonetetracarboxylic dianhydride and 2.1 mol of allyl carbinol were added to 2 L of N-methyl-2-pyrrolidone and stirred in a reaction flask equipped with a nitrogen introducing tube. Then, 2.1 mol of triethylamine is continuously added dropwise over 30 minutes. This state was left for 3 hours. Next, 0.9 mol of metaphenylenediamine
And 1,3-bis (γ-aminopropyl) -1,1,3
3-tetramethyldisiloxane 0.1 mol and added 3
After stirring for 0 minutes, 3.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added in 3 portions, and the condensation reaction is performed for 3 hours in that state. The reaction solution is poured into a large amount of methanol for reprecipitation, and a large amount of methanol is further added to the obtained slurry mixture for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. Further, 20 g of dried solid resin, 1 g of N-phenylglycine, 3 g of triallyl isocyanurate, and 1 g of triazinetrithiol were dissolved in 40 g of N-methyl-2-pyrrolidone, and the resulting solution was filtered to 1 μm to obtain sample 1 And

An 8-inch silicon wafer was coated with this sample 1 using a spin coater, and dried by heating on a baking plate at 90 ° C. for 3 minutes to obtain a coating film having a film thickness of 8 μm. This coating film was exposed to 100 mj / m by an ultraviolet light exposure device using a filter that transmits only 365 nm.
A test pattern was irradiated with an energy of cm ² , paddle development was performed for 1 minute with cyclohexanone, cleaning was performed with isopropyl alcohol, and spin drying was performed. By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was 5.0 μm.
It was confirmed that the pattern up to m was formed sharply.

Further, this pattern was subjected to heat treatment at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern. The film thickness after curing was 5 μm, and the film reduction rate from coating to curing was 62.5%.

Sample 1 was coated on a 6-inch silicon wafer on which copper wiring was drawn, and a baking plate was used for 90.
A coating film having a film thickness of 8 μm was obtained by heating and drying at 3 ° C. for 3 minutes. This coating film is 100 mj / cm by an ultraviolet exposure device using a filter that transmits only 365 nm.
Irradiate the test pattern with energy of ² , perform paddle development for 1 minute with cyclohexanone, wash with isopropyl alcohol, spin dry, 150 ° C
For 1 hour, at 250 ° C. for 1 hour, and at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and when conduction of the copper wiring was confirmed, there was no deterioration such as disconnection.

Further, Sample 1 was coated on a copper plate and heated and dried at 90 ° C. for 3 minutes on a baking plate to obtain a coating film having a film thickness of 8 μm. This coating film is exposed by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiate a test pattern with energy of 00 mj / cm ² , perform paddle development for 1 minute with cyclohexanone,
The film was washed with isopropyl alcohol, spin-dried, and heat-treated at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and 350 ° C. for 1 hour to complete imidization of the coating film. The adhesive strength between this coating film and the copper plate is determined by JIS
When confirmed by the cross-cut tape method in K-5400, no peeling was observed.

Example 2 First, 1.0 mol of biphenyltetracarboxylic dianhydride and 2.1 mol of allylcarbinol were added to 2 L of N-methyl-2-pyrrolidone in a reaction flask equipped with a nitrogen introducing tube. Stir and subsequently add 2.1 mol of triethylamine dropwise over 30 minutes. This state was left for 3 hours. Next, 0.9 mol of 9,9-bis (4-aminophenyl) fluorene and 0.1 mol of 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added to 30 mol. After stirring for 3 minutes, 3.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added in 3 batches, and the condensation reaction is continued for 6 hours in this state. The reaction solution is poured into a large amount of methanol for reprecipitation, and a large amount of methanol is further added to the obtained slurry mixture for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. Further dried solid resin 20g, N-phenylglycine 1.2g and triallyl isocyanurate 4g
And 2 g of triazinetrithiol were dissolved in 30 g of N-methyl-2-pyrrolidone, and the resulting solution was filtered by 1 μm to obtain Sample 2.

A 6-inch silicon wafer was coated with this sample 2 by using a spin coater, and dried by heating on a baking plate at 90 ° C. for 4 minutes to give a film thickness of 13 μm.
A coating film of This coating film was exposed to 200 mj by an ultraviolet exposure machine using a filter that transmits only 365 nm.
The test pattern was irradiated with an energy of 1 / cm ² and heated at 90 ° C. for 1 minute on a bake plate, then paddle development was performed for 1 minute with γ-butyrolactone, washed with propylene glycol monomethyl ether acetate, and spin-dried. . By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was confirmed that a pattern with a size of 8.0 μm was sharply formed.

Further, this pattern was subjected to a heat treatment at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern. The film thickness after curing was 8 μm, and the film reduction rate from coating to curing was 61.5%.

Further, the sample 2 was coated on a 6-inch silicon wafer on which copper wiring was drawn, and 90
A coating film having a film thickness of 13 μm was obtained by heating and drying at 4 ° C. for 4 minutes. This coating film was exposed to 200 mj / c by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiate the test pattern with the energy of m ² , perform paddle development with γ-butyrolactone for 1 minute, wash with propylene glycol monomethyl ether acetate, spin dry, 150 ° C. for 1 hour, then 25
Heat treatment was carried out at 0 ° C. for 1 hour and at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and when conduction of the copper wiring was confirmed, there was no deterioration such as disconnection.

Further, Sample 2 was coated on a copper plate and heated and dried at 90 ° C. for 4 minutes on a baking plate to obtain a coating film having a film thickness of 13 μm. This coating film is irradiated with a test pattern with an energy of 200 mj / cm ² by an ultraviolet exposure machine using a filter that transmits only 365 nm, and paddle development is performed with γ-butyrolactone for 1 minute, and washed with propylene glycol monomethyl ether acetate. Then, spin drying was performed, and heat treatment was performed at 150 ° C. for 1 hour, at 250 ° C. for 1 hour, and at 350 ° C. for 1 hour to complete imidization of the coating film. When the adhesive strength between the coating film and the copper plate was confirmed by the cross-cut tape method in JIS-K-5400, no peeling was observed.

Comparative Example 1 First, 1.0 mol of benzophenonetetracarboxylic dianhydride and 2.1 mol of ethylhexyl methacrylate were added to 2 L of N-methyl-2-pyrrolidone and stirred in a reaction flask equipped with a nitrogen introducing tube. , 2.1mo in a row
1 of triethylamine is added dropwise over 30 minutes. This state was left for 3 hours. Next, 0.9 mol of metaphenylenediamine and 1,3-bis (γ-aminopropyl)-
1,1,3,3-tetramethyldisiloxane 0.1mo
After adding 1 and stirring for 30 minutes, 3.0 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added in 3 batches and the condensation reaction is carried out for 3 hours in that state. The reaction solution is poured into a large amount of methanol for reprecipitation, and a large amount of methanol is further added to the obtained slurry mixture for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. 20 g of dried solid resin and 1 g of N-phenylglycine
And 3 g of trimethylolpropane trimethacrylate were dissolved in 40 g of N-methyl-2-pyrrolidone, and the resulting solution was filtered by 1 μm to obtain Sample 3.

An 8-inch silicon wafer was coated with this sample 3 using a spin coater, and dried by heating on a baking plate at 90 ° C. for 3 minutes to obtain a coating film having a film thickness of 8 μm. This coating film was exposed to 100 mj / m by an ultraviolet light exposure device using a filter that transmits only 365 nm.
A test pattern was irradiated with an energy of cm ² , paddle development was performed for 1 minute with cyclohexanone, cleaning was performed with isopropyl alcohol, and spin drying was performed. By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was 6.0 μm.
It was confirmed that the pattern up to m was formed sharply.

Further, this pattern was heat-treated at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern. The film thickness after curing was 4 μm, and the film reduction rate from coating to curing was 50%.

Sample 3 was coated on a 6-inch silicon wafer on which copper wiring was drawn, and a baking plate was used for 90.
A coating film having a film thickness of 10 μm was obtained by heating and drying at 3 ° C. for 3 minutes. This coating film was exposed to 100 mj / c by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiate the test pattern with energy of m ² , perform paddle development for 1 minute with cyclohexanone, wash with isopropyl alcohol, spin dry,
1 hour at ℃, then 1 hour at 250 ℃, 350 ℃
Was heat-treated for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and when conduction of the copper wiring was confirmed, there was no deterioration such as disconnection.

Further, Sample 3 was coated on a copper plate and heated and dried on a baking plate at 90 ° C. for 3 minutes to obtain a coating film having a film thickness of 10 μm. This coating film is irradiated with a test pattern with an energy of 100 mj / cm ² by an ultraviolet exposure device using a filter that transmits only 365 nm, paddle development is carried out for 1 minute with cyclohexanone, washed with isopropyl alcohol, and spin-dried. Then, heat treatment was performed at 150 ° C. for 1 hour, at 250 ° C. for 1 hour, and at 350 ° C. for 1 hour to complete imidization of the coating film. The adhesive force between this coating film and the copper plate,
When checked by the cross-cut tape method in JIS-K-5400, 80% or more of the cross-cuts were peeled off.

Comparative Example 2 First, 0.9 mol of 9,9-bis (4-aminophenyl) fluorene and 1,3-bis (γ-aminopropyl) -1,1, were placed in a reaction flask equipped with a nitrogen introducing tube. 3,3
-0.1 mol of tetramethyldisiloxane and 3 L of N
-Methyl-2-pyrrolidone is added and dissolved by stirring. Continuously 1.0 mol of biphenyl tetracarboxylic dianhydride
Is dripped in 10 minutes. This state was left for 3 hours. Next, the reaction solution was heated to 70 ° C. and left for 3 hours,
Cool to room temperature. To this reaction solution, 60 g of N-phenylglycine and 370 g of N, N-diethyl-ethylmethacrylateamine were added and dissolved. The resulting solution is 1 μm
Filtered to sample 4. A 6-inch silicon wafer was coated with this sample 4 using a spin coater, and dried by heating on a baking plate at 90 ° C. for 4 minutes to obtain a coating film having a film thickness of 13 μm. This coating is 365nm
A test pattern is irradiated with an energy of 300 mj / cm ² using an ultraviolet light exposure device that uses a filter that allows only light to pass through, paddle development is performed for 1 minute with N-methyl-2-pyrrolidone, washed with isopropyl alcohol, and spin-dried I went. By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was confirmed that a pattern of up to 20.0 μm was sharply formed.

Further, this pattern was subjected to a heat treatment at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern. The film thickness after curing was 7 μm, and the film reduction rate from coating to curing was 53%.

Sample 4 was coated on a 6-inch silicon wafer on which copper wiring was drawn, and baked on a bake plate for 90 minutes.
A coating film having a film thickness of 13 μm was obtained by heating and drying at 4 ° C. for 4 minutes. This coating film was exposed to 300 mj / c by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiate the test pattern with energy of m ² , perform paddle development with N-methyl-2pyrrolidone for 1 minute, wash with isopropyl alcohol, spin dry, 150 ° C. for 1 hour, then 250 ° C. for 1 hour. Further, heat treatment was performed at 350 ° C. for 1 hour to complete imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, but the copper wiring was corroded and discolored, and electrical continuity was confirmed, but no electrical signal could be detected.

Further, Sample 4 was coated on a copper plate and heated and dried at 90 ° C. for 4 minutes on a baking plate to obtain a coating film having a film thickness of 13 μm. This coating film is irradiated with a test pattern with an energy of 200 mj / cm ² by an ultraviolet light exposure device using a filter that transmits only 365 nm, and paddle development is performed for 1 minute with N-methyl-2pyrrolidone, and washed with isopropyl alcohol. Then, spin drying was performed, and heat treatment was performed at 150 ° C. for 1 hour, at 250 ° C. for 1 hour, and at 350 ° C. for 1 hour to complete imidization of the coating film. When the adhesive strength between the coating film and the copper plate was confirmed by the cross-cut tape method in JIS-K-5400, all cross-cuts were peeled off.

[0052]

INDUSTRIAL APPLICABILITY The present invention is a photosensitive polyimide precursor capable of forming a negative pattern, and not only can obtain an extremely sharp high-resolution pattern, but also has the advantage of shortening the process due to photosensitivity and It is possible to completely eliminate mutagenic toxic chemicals that were generated in large quantities.

The present invention relates to the resin skeleton itself used in the photosensitive resin composition and a method for producing the same, but these are based on a completely new idea, and are extremely excellent unlike any other. It is easy to understand that this is a different invention.

Claims (2)

[Claims] 1. (A) a polyimide precursor having the following repeating units: (In the formula, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO—, —SO. ₂ -, - CH ₂ - or -
A tetravalent organic group bonded by C (CF ₃ ) ₂
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
Is a divalent aromatic group bonded with-, R ³ and R ⁴ are
An organic group having an αβ unsaturated bond as well as being bonded via a hydroxyl group or —O— or —NH—,
And n is an integer of 1 or more) (B) A polyfunctional polyene compound represented by the following general formula: embedded image R ⁵ — (CH═CH ₂ ) _m (wherein, R ⁵ is m αβ unsaturated bond is a single bond or an organic group bonded via —O—, —CO—, —CH ₂ —, —SO ₂ — or —NH—, and m is 2 to
(C is an integer of 4) (C) A polyfunctional thiol compound represented by the following general formula: embedded image R ⁶ — (CH ₂ —SH) _x (wherein, R ⁶ is 1 to 3) thiol groups, a single bond or -O -, - CO -, - CH 2 -, - SO 2 - a or an organic group bonded to -NH-, x is an integer of 1 to 3) (D) A photosensitive resin composition comprising a dehydration condensing agent used for producing the polyimide precursor, (E) a photosensitizer used for improving sensitivity to actinic rays, and (F) a solvent. 2. (1) R shown in the repeating unit of the following formula
Step of esterification reaction between acid dianhydride having ^one skeleton and a compound having an αβ unsaturated bond of R ³ and R ^{4 in} the skeleton, (In the formula, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO—, —SO. ₂ -, - CH ₂ - or -
A tetravalent organic group bonded by C (CF ₃ ) ₂
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings are —O—, —CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
Is a divalent aromatic group bonded with-, R ³ and R ⁴ are
An organic group having an αβ unsaturated bond as well as being bonded via a hydroxyl group or —O— or —NH—,
And n is an integer of 1 or more. (2) Polycondensation reaction step of the esterification reaction product of (1) and the diamine compound having the R ² skeleton in Formula 4 under the addition of the dehydration condensation agent. , (3) a polycondensation reaction of the polyimide precursor, and (4) a polyfunctional polyene compound represented by the following general formula: embedded image wherein R ⁵ — (CH═CH ₂ ) _m (wherein , R ⁵ is an organic group in which m αβ unsaturated bonds are bonded via a single bond or —O—, —CO—, —CH ₂ —, —SO ₂ — or —NH—, and m is 2 to
Is an integer of 4) and a polyfunctional thiol compound represented by the following general formula and R ^6- (CH ₂ -SH) _x (wherein R ⁶ is 1 to 3 thiol groups) but a single bond or -O -, - CO -, - CH 2 -, - SO 2 - or an organic group bonded to -NH-, x is an integer of 1 to 3) improved the sensitivity to active light A method for producing a photosensitive resin composition, which comprises the step of preparing a polyimide precursor solution containing a photosensitizer used for the purpose.