JPH05134406A - Production of semiconductor device - Google Patents

Abstract

PURPOSE:To easily form a heat resistant photosensitive resin pattern with a high resolution at a high throughput by compounding N-phenyl glycine and its deriv. and thiol compd. with specific ester polyamido and sticking them on the semiconductive device, baking the circuit, developing and curing. CONSTITUTION:The photosensitive resin compsn. consisting essentially of the ester polyamide expressed by formula I, the N-phenyl glycine expressed by formula II and its deriv. and the thiol compds. is stuck at 2 to 30mum film thickness on the surface of the semiconductor element, is exposed by a monochromatic light exposing machine of 365nm or I-ray stepper and is developed to form patterns. The resin compsn. is then cured by heating at >=300 deg.C and <=450 deg.C. In the formula I, R1 to R4 denote the group expressed by formula III; 1 to m denote 0 or 1; p denotes an integer from 1 to 5; x to z denote (per cent of respective constitutional units) 0<x, y<100, 0<Z<80 and x+y+z=100. In the formula III, R5 denotes bivalent to hexad org. groups; R6 denotes H or CH3 group. In the formula II, R7 denotes -H, -CH3, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a photosensitive resin having excellent photosensitivity to I-ray light, particularly good sensitivity, which is adhered onto a semiconductor device and exposed by an I-line stepper.
It is possible to easily prepare a heat-resistant photosensitive resin pattern having a high throughput and a high resolution which has never been seen before.

[0002]

2. Description of the Related Art Conventionally, a polyimide having excellent heat resistance and excellent electrical insulation and mechanical strength has been used for a surface protective film and an interlayer insulating film of a semiconductor element. Recently, a technique for imparting photosensitivity to the polyimide itself has been attracting attention in order to simplify the complicated process. For example, the following formula

[0003]

[Chemical 3]

A polyimide precursor composition having a photosensitive group with an ester group having a structure shown by
55-41422) and the like are known. All of these are dissolved in a suitable organic solvent, applied in a varnish state, dried, irradiated with ultraviolet rays through a photomask, developed, rinsed to obtain a desired pattern, and further heated to form a polyimide. It is a film.

The use of a photosensitized polyimide not only has the effect of simplifying the pattern forming process, but it is also safe and excellent in pollution because it does not require the use of a highly toxic etching solution. It is expected that sexualization will become an even more important technology in the future. However, when such a conventional photosensitizing technique is applied, in a photosensitive polyimide resin composition obtained by adding a conventional photoinitiator to a polyimide precursor having a photosensitive group provided with an ester group, I-line light (generated by a mercury lamp) However, when exposed by an I-line stepper exposure machine, it requires a long irradiation time, and its practicality is low.

[0006]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polyamic acid ester in which a mono- or polyfunctional photosensitive group and a lower alcohol are introduced into an ester bond to a carboxyl group in a specific polyamic acid. , N-phenylglycine and its derivatives and thiol compounds are mixed to deposit a photosensitive resin composition having extremely good sensitivity to I-ray light on a semiconductor device, and a 365 nm monochromatic light exposure device or I Another object of the present invention is to provide a method for manufacturing a semiconductor device obtained by baking, developing and curing a circuit with high throughput using a line stepper.

[0007]

The present invention is based on the formula (1):

[0008]

[Chemical 1]

A polyamic acid ester represented by (B)
Formula (2)

[0010]

[Chemical 2]

A photosensitive resin composition containing N-phenylglycine and its derivative represented by (C) and thiol compounds (C) as essential components is adhered to the surface of a semiconductor device in a film thickness of 2 to 30 μm, and a monochromatic light of 365 nm is emitted. A pattern is formed by exposing and developing with an exposure machine or an I-line stepper, and then 300 ° C or higher and 450 ° C
The following is a method for manufacturing a semiconductor device, characterized in that it is heat-cured.

[0012]

The specific polyamic acid ester represented by the formula (1) used in the present invention has a high light transmittance in the near-ultraviolet region, exhibits a high reactivity with a radical initiator, and has a good cured product. It has heat resistance, mechanical properties, and electrical properties.

In the formula (1), R ₁ is

[0014]

[Chemical 4]

## STR1 ## These are generally introduced by pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride or a derivative thereof. In use, one kind or a mixture of two or more kinds may be used. Also, some other organic groups may be used to further improve the properties of the cured product. For example, trimellitic anhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride,
Naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride , Naphthalene-1,
2,6,7-Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,
3,5,6,7-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2 , 3,6,7-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6, 7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2',
3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'
-Diphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -p-
Terphenyl tetracarboxylic dianhydride, 2,2 ", 3,3" -p-
Terphenyl tetracarboxylic dianhydride, 2,3,3 ", 4" -p-
Terphenyl tetracarboxylic dianhydride, 2,2-bis (2,3
-Dicarboxyphenyl) -propane dianhydride, 2,2-bis
(3,4-dicarboxyphenyl) -propane dianhydride, bis
(2,3-dicarboxyphenyl) ether dianhydride, bis
(3,4-dicarboxyphenyl) ether dianhydride, bis
(2,3-dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3- Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-
Tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12 -Tetracarboxylic acid dianhydride, phenanthrene-1,2,7,8-tetracarboxylic acid dianhydride, phenanthrene-1,2,6,7-tetracarboxylic acid dianhydride, phenanthrene-1,2,9, 10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3, 4,5-tetracarboxylic dianhydride,
Examples thereof include, but are not limited to, thiophene-2,3,4,5-tetracarboxylic dianhydride. Further, in use, one kind or a mixture of two or more kinds may be used.

In the formula (1), R ₂ is

[0017]

[Chemical 5]

An organic group represented by
-Diaminodiphenyl ether or its derivatives are used. Also, some other organic groups may be used to improve the properties of the cured product. For example, m-phenylene-diamine, 1-isopropyl-2,4-phenylene-diamine, p-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'- Diamino-diphenylethane, 3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-
Diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl ether , Benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4 '
-Diamino-biphenyl, 3,3'-dimethoxy-benzidine,
4,4 "-diamino-p-terphenyl, 3,3" -diamino-p-terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-
β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-5-amino-pentyl) benzene, 1,5-diamino -Naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino-
t-butyl) toluene, 2,4-diamino-toluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,6- Diamino
-Pyridine, 2,5-diamino-pyridine, 2,5-diamino-1,
3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2-dimethyl-propylene-
Diamine, tetramethylene-diamine, pentamethylene-
Diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine, 3-methoxy-hexamethylene-
Diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,4-dimethyl-heptamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl -Nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino-
1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12
-Diamino-octadecane, 2,12-diamino-octadecane, 2,17-diamino-icosane, diaminosiloxane,
Examples thereof include 2,6-diamino-4-carboxylic benzene and 3,3′-diamino-4,4′-dicarboxylic benzidine, but are not limited thereto. In use, one kind or a mixture of two or more kinds may be used.

In the formula (1), R ₃ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups, R ₄ is a photosensitive group having 1 to 5 acrylic (methacrylic) groups or a methyl group, It is an ethyl group. Acrylic (methacrylic) group is 0 in R ₃ and R _4.
Is not preferable because a crosslinked structure cannot be obtained. Further, 6 or more acryl (methacryl) groups are not preferable because not only industrially difficult to manufacture, but also the compatibility becomes low because the molecular weight becomes large. As a compound for introducing R ₃ and R ₄ ,
For example, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycerol diacrylate,
Glycerol dimethacrylate, glycerol acrylate methacrylate, trimethylolpropane diacrylate, 1,3-diacryloylethyl-5-hydroxyethyl isocyanurate, 1,3-dimethacrylate-5-hydroxyethyl isocyanurate, ethylene glycol-modified pentaerythritol triacrylate Acrylate, propylene glycol modified pentaerythritol triacrylate,
Trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, polyethylene glycol modified methacrylate, polyethylene glycol modified Acrylate, polypropylene glycol modified acrylate, polypropylene glycol modified methacrylate, etc.
It is not limited to these. In using these, one kind or a mixture of two or more kinds may be used. The methyl group or ethyl group of R ₄ is usually derived from methanol, ethanol or the like.

The polyamic acid ester represented by the formula (1) used in the present invention, the proportion of the structural unit R ₃ is introduced into the carboxyl group is x, a part in R _3, R ₄ is introduced into the remaining The ratio of the structural units is y, the ratio of the structural units in which the carboxyl group is substituted with R ₄ is z, and three types of structural units are mixed. 0 <x, y <100, 0 <z <respectively
It is 80 and satisfies x + y + z = 100, and x, y, and z represent the percentage of each structural unit. R ₄ is -CH ₃ or -C
_In the case of ₂ H ₅ , when z is 80 or more, the amount of the photosensitive group is small, the sensitivity is low, and the practicality is low.

The polyamic acid ester (A) in the present invention is usually synthesized as follows. First, a multifunctional photosensitive group R ₃ , and in some cases, a compound having an alcohol group for introducing R ₄ is dissolved in a solvent, and excess pyromellitic dianhydride and / or 3,3 ′, 4, The 4'-benzophenone tetracarboxylic dianhydride or its derivative is reacted. Thereafter, the remaining carboxyl group and acid anhydride group can be reacted with diamine to synthesize.

The (B) N-phenylglycine and its derivatives in the present invention are decomposed by ultraviolet rays, especially I-ray light,
It serves to generate radicals efficiently. N-phenylglycine and its derivatives are N-phenylglycine, N- (p-
Methyl) phenylglycine, N- (p-ethyl) phenylglycine, N- (p-methoxy) phenylglycine, N- (p-chloro)
Phenylglycine, N- (p-nitro) phenylglycine, N-
(p-dimethylamino) phenylglycine, N- (p-bromo) phenylglycine, N- (p-acetoxy) phenylglycine,
N- (p-hydroxy) phenylglycine and its ortho isomers and meta isomers. Generally, the amount of N-phenylglycine and its derivative added is 3 to 15 parts by weight per 100 parts by weight of the polyamic acid ester (A). If it is 3 parts by weight or less, the sensitivity is lowered, which is not preferable. On the other hand, if it is 15 parts by weight or more, the preservability is deteriorated and the photosensitive resin composition is apt to gel, which is not preferable.

The (C) thiol compound in the present invention is a general term for compounds having a --SH group, and the addition of the thiol compound further improves the sensitivity and the storage stability. As the thiol compound, 1-
Phenyl-5-mercapto-1H-tetrazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, pentaerythritol tetrakis- (thioglycolate), thioglycolic acid, ammonium thioglycolic acid, thioglycolic acid Butyl, octyl thioglycolate, methoxybutyl thioglycolate, trimethylolpropane tris- (thioglycolate), ethylene glycol dithioglycolate, β-mercaptopropionic acid, octyl β-mercaptopropionate, trimethylolpropane tris- (β
-Thiopropionate), pentaerythritol tetrakis- (β-thiopropionate), 1,4-butanediol dithiopropionate, thiosalicylic acid, furfuryl mercaptan, benzyl mercaptan, α-mercaptopropionic acid, p-hydroxy Examples thereof include, but are not limited to, thiophenol, p-methylthiophenol, and thiophenol. Among these thiol compounds, 1-phenyl-5-mercapto-1H-tetrazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are more preferable because they have a particularly large effect of improving sensitivity. The amount of the thiol compounds (C) compounded is the polyamic acid ester (A)
0.3 to 3 parts by weight is preferable for 100 parts by weight. If it is 0.3 parts by weight or less, the effect of improving the sensitivity is small and it is not preferable. Further, if it is 3 parts by weight or more, the solubility is lowered and the storage stability is lowered, which is not preferable.

Further, in the present invention, a sensitizer other than these may be used in combination. For example,

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

Examples thereof include, but are not limited to: In addition, one kind or a mixture of two or more kinds may be used. The addition amount of the photosensitizer is 0.1-10 with respect to 100 parts by weight of the polyamic acid ester (A).
Parts by weight are preferred. If it is 0.1 part by weight or less, the amount of addition is too small and it is difficult to obtain the effect of improving the sensitivity. Above 10 parts by weight,
The sensitizer in the system lowers the strength of the cured film, which is not preferable.

To the photosensitive resin composition used in the present invention, an adhesion aid, an inhibitor, a leveling agent and other various fillers may be added.

To deposit the photosensitive resin composition used in the present invention on a semiconductor device, spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating and the like are usually performed. Then 60-140
Pre-bake at ° C to dry the coating. The thickness of the coating film obtained by drying is preferably 2 to 30 μm. When the thickness is 2 μm or less, the final film thickness after curing is 1 μm or less, and pinholes are easily generated, which is not preferable. On the other hand, if it is 30 μm or more, the exposure amount in the circuit printing step is large, which is unpractical, which is not preferable.

The photosensitive resin thus obtained was mixed with
The semiconductor device attached to a thickness of -30 μm is printed with a 365 nm monochromatic exposure machine or an I-line stepper. These light irradiators are devices that are indispensable for semiconductor device manufacturing, and are now becoming mainstream. By using these apparatuses, it is possible to use the same exposure apparatus that is used as a general apparatus for manufacturing semiconductor devices, and it is possible to significantly reduce equipment.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. As a developing solution, N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N
-Use dimethylformamide, etc., methanol, isopropyl alcohol, water, alkaline aqueous solution, etc. alone or as a mixture. As the developing method, methods such as spraying, paddle, dipping, and ultrasonic wave can be used.

Next, the relief pattern formed by development is rinsed. As the rinse liquid, methanol, xylene, ethanol, isopropyl alcohol, butyl acetate, water or the like is used. Next, heat treatment is performed to form an imide ring, and a final pattern having high heat resistance is obtained.

The curing temperature is preferably 300 ° C or higher and 450 ° C or lower. When the temperature is 300 ° C or lower, the imide ring closure does not reach 100%,
It is not preferable because heat resistance and the like decrease. When the temperature is 450 ° C. or higher, decomposition starts and mechanical strength decreases, which is not preferable. Also, by attaching this photosensitive resin composition to a semiconductor device, the moisture resistance and the like of the semiconductor device is improved.

[0036]

The present invention will be specifically described with reference to the following examples. (Example 1) 65.5 g (0.30 mol) of pyromellitic dianhydride and 225.5 g (0.70 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were combined with 2-hydroxy-1, After esterifying the carboxyl group with 456 g (2.00 mol) of 3-dimethacryloxypropane, 170.2 g (0.85 mol) of 4,4'-diaminodiphenyl ether was used as a condensing agent for dicyclohexylcarbodiimide to obtain a polyamic acid ester copolymer. .. The dicyclohexylurea was separated by filtration and then reprecipitated in ethanol, and the solid matter was filtered and dried under reduced pressure. To 100 parts by weight of this polyamic acid ester, N-phenylglycine 6 parts by weight, 1-phenyl-5-mercapto-1H-tetrazole 1 part by weight, tetraethylene glycol dimethacrylate 10 parts by weight and methyl ether hydroquinone 0.1 parts by weight N- It was dissolved in 150 parts by weight of methyl-2-pyrrolidone to obtain a photosensitive resin composition.

The resulting solution was applied onto a silicon wafer having an aluminum circuit having a width of 2 μm with a spinner and dried at 70 ° C. for 1 hour by a dryer. The film thickness of the photosensitive resin composition was 15.0 μm. Wafers with this photosensitive resin composition adhered to 200mJ / c with 1/5 reduced I-line stepper (NA; 0.45)
The exposure was increased from m ² by 5 mJ / cm ² per one shot. The total number of shots is 64,
It was exposed from 200mJ / cm ² to 520mJ / cm ^2.

Next, development was performed by spraying with a developing solution containing 60% by weight of N-methylpyrrolidone and 40% by weight of xylene, rinsed with isopropyl alcohol, and further dried at 150 ° C. in a nitrogen drier controlled to have an oxygen concentration of 20 ppm or less. , 250
C., 350.degree. C., 30 minutes each, to obtain a semiconductor device. The pattern of the obtained semiconductor device is clear regardless of the exposure and
It had a taper angle of ~ 70 ° and was deposited with a thickness of 7.9 μm. This semiconductor device is 125
It was exposed to saturated steam at ℃ for 500 hours.
(It is abbreviated as 00 hours later), it was found that the conduction failure rate was extremely low at 0.8%.

(Example 2) 2-hydroxy-1,3 of Example 1
-Dimethacryloxypropane 456 g (2.00 mol) 228 g (1.
The amount was reduced to 00 mol), and 32 g (1.00 mol) of methanol was added and reacted. Otherwise, the same operation as in Example 1 is performed,
A photosensitive resin composition was obtained and the same evaluation was performed. The pattern of the obtained semiconductor device is clear regardless of the exposure dose and
It had a taper angle of ~ 80 ° and a film thickness of 7.6 μm. The defective rate of this semiconductor device after 500 hours of PCT was as low as 0.5%.

(Example 3) 2-hydroxy-1,3 of Example 1
-Dimethacryloxypropane was changed to 240 g (2.00 mol) of 2-hydroxyethyl methacrylate to obtain a resin composition, and the same evaluation was performed. The pattern of the obtained semiconductor device is clear, has a taper angle of 55 to 60 °, and has a film thickness of 7.7.
It was μm. The defective rate of this semiconductor device after PCT 500 hours was as low as 0.6%.

(Example 4) The N-phenylglycine of Example 1 was changed to N-4-chlorophenylglycine to obtain a resin composition, and the same evaluation was carried out. The pattern of the obtained semiconductor device is clear, has a taper angle of 65 to 70 °, and the film thickness is
It was 8.2 μm. The defective rate of this semiconductor device after 500 hours of PCT was as low as 0.9%.

(Example 5) The 1-phenyl-5-mercapto-1H-tetrazole of Example 1 was changed to 2-mercaptobenzoxazole to obtain a resin composition, and the same evaluation was carried out. The pattern of the obtained semiconductor device is clear and 60 to 70
It had a taper angle of ° and the film thickness was 7.6 μm. The defective rate of this semiconductor device after 500 hours of PCT was as low as 0.4%.

Comparative Example 1 N-phenylglycine and 1-phenyl-5-mercapto-1H-tetrazole of Example 1 were changed to 5 parts by weight of Michler's ketone (absorption maximum wavelength 365 nm) to obtain a resin composition. .. Similarly, an attempt was made to manufacture a semiconductor device, but no pattern was obtained at an exposure dose of 470 mJ / cm ² or less, and the semiconductor device was about to be peeled off even at an exposure dose of more than that. After curing this, PCT treatment was performed.
After 0 hours, it was completely peeled off, and the conduction failure rate was as high as 93%, which proved to be impractical.

(Comparative Example 2) 2-hydroxy-1,3 of Example 1
-Dimethacryloxypropane was changed to 92 g (2.00 mol) of ethanol to obtain a resin composition, and the same evaluation was performed. It was found that the obtained semiconductor device was not practical because the resin composition pattern was not eluted and attached during development.

Comparative Example 3 The same photosensitive resin composition as in Example 1 was obtained, and the photosensitive resin composition was adhered onto a semiconductor device so that the film thickness was 1.5 μm, and the same evaluation was carried out. The pattern of the obtained semiconductor device was clear, but the taper angle was as wide as 30 to 40 °. The film thickness was as thin as 0.7 μm. The defective rate of this semiconductor device after PCT 500 hours was as high as 12.6%.

(Comparative Example 4) The same evaluation was performed by changing the film thickness on the semiconductor device of Example 1 to 40 μm. It was found that the obtained semiconductor device collapsed without forming a precise pattern, the taper angle and the film thickness could not be measured, and it was not practical.

(Comparative Example 5) The curing temperature of Example 1 was set to 250 ° C.
The same evaluation was carried out. The pattern of the obtained semiconductor device was clear, had a taper angle of 75 to 85 °, and had a film thickness of 8.4 μm. However, the PCT50 of this semiconductor device
After 0 hours, the photosensitive resin film was peeled off, and the defect rate was as high as 23.3%.

Comparative Example 6 The curing temperature of Example 1 was 500 ° C.
The same evaluation was carried out. It was found that the obtained semiconductor device was impractical because the photosensitive resin portion was partially carbonized and destroyed, and the taper angle and the film thickness could not be measured.

[0049]

EFFECTS OF THE INVENTION Conventionally, a technique of introducing a photosensitive group into a carboxyl group of a polyamic acid in the form of an ester has been known.
It was found to have low sensitivity to 5 nm or I-line light. In the present invention, a polyamic acid ester in which a photosensitive group is bound to a carboxyl group of a specific polyamic acid in an ester form, N-
It was found that by adding phenylglycine and its derivatives and thiol compounds, the photoradical initiation reaction can be easily and efficiently performed with respect to 365 nm light, and the sensitivity is significantly improved. Therefore, it was found for the first time that a photosensitive resin composition having heat resistance could be patterned by an I-line stepper with a practical exposure amount.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/038 504 H01L 21/027 21/312 B 8518-4M

Claims (1)

[Claims] 1. Photosensitivity comprising (A) a polyamic acid ester represented by the formula (1), (B) N-phenylglycine represented by the formula (2) and a derivative thereof, and (C) a thiol compound as essential components. 2-30 μm of resin composition on the surface of semiconductor element
To form a pattern by exposing and developing with a 365 nm monochromatic light exposure device or I-line stepper
A method of manufacturing a semiconductor device, which comprises heat-curing at a temperature of not less than 450 ° C and not more than 450 ° C. [Chemical 1] [Chemical 2]