JPH10204291A - Heat treatment of photosensitive heat-resistant resin precursor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve mechanical characteristics such as elongation of a heat- resistant resin film of a polyimide film, by exposing a photosensitive heat- resistant resin precursor composition to the light, developing and heat-treating the developed composition in an specific oxygen concentration atmosphere. SOLUTION: A positive type photosensitive heat-resistant resin precursor composition is applied to a substrate such as a silicon wafer, dried at 50-150 deg.C for 1 minute to several hours and exposed to the light by irradiation with chemical rays. Then, composition is developed and heat-treated in an atmosphere having <=100ppm, preferably <=20ppm oxygen concentration, for example, at 140 deg.C, 200 deg.C and 350 deg.C for 30 minutes, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for heat-treating a photosensitive heat-resistant resin precursor.

[0002]

2. Description of the Related Art In the field of semiconductors, photosensitive heat-resistant resin precursors are used for forming interlayer insulating films, buffer coat films, alpha ray shielding films, and the like. One of the major features of the photosensitive heat-resistant resin precursor is that it can be patterned by developing it after irradiation with actinic radiation. Then, the pattern of the heat-resistant resin can be easily obtained by heat-treating the obtained pattern. However, since the photosensitive heat-resistant resin precursor contains this photosensitive component, when heat treatment is performed in the air, the photosensitive component undergoes a crosslinking reaction by heat and oxygen,
Since the oxidative decomposition reaction occurs, there is a problem that the mechanical properties are significantly reduced.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and has as its object to improve the mechanical properties of a heat-resistant resin film of a photosensitive heat-resistant resin precursor. The purpose is to provide a method of causing the

[0004]

That is, according to the present invention, a photosensitive heat-resistant resin precursor is exposed and developed, and then an oxygen concentration of 100 p.
A heat treatment method for a photosensitive heat-resistant resin precursor, wherein the heat treatment is performed in an atmosphere of not more than pm.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the heat treatment of the present invention, the oxygen concentration of the atmosphere during the heat treatment is set to 100 ppm or less, preferably 50 ppm.
pm or less, more preferably 20 ppm or less, to suppress the oxidative cross-linking reaction of the photosensitive component that decomposes and goes out of the film, and to greatly improve the mechanical properties, particularly elongation, of the resulting heat-resistant resin film. Can be.

As the photosensitive heat-resistant resin precursor, a composition in which a photosensitive group is introduced by ionic bonding into a polyamic acid known as a photosensitive polyimide precursor, and a composition in which an ester group is introduced into a polyamic acid with photosensitivity. And the like, but are not limited thereto. Such a photosensitive polyimide precursor composition is commercially available under the names of "Toray Co., Ltd." Photo Nice ", Asahi Kasei Co., Ltd." Pimeru ", Hitachi Chemical Co., Ltd." Photopal ", Dupont" Pyralin "and the like. The present invention is effective for these, but is particularly effective in the heat treatment of the ester type photosensitive polyimide precursor.

[0007] As the photosensitive heat-resistant resin precursor,
A composition obtained by adding a nifedipine compound to a polyamic acid that is a photosensitive polyimide precursor, a solution obtained by adding orthonaphthoquinonediazide sulfonate to a soluble polyimide having a phenolic hydroxyl group, and a carboxylic acid of a polyamic acid having a group that can be removed by an acid. A mixture of a polyamic acid ester protected with an acid and a photoacid generator, a mixture of a polyhydroxyamidamic acid and an orthonaphthoquinonediazide sulfonic acid ester, a photosensitive polybenzoxazole precursor, and a polyhydroxyamide with an orthonaphtho. Examples thereof include quinonediazidesulfonic acid esters. Particularly, in the case of a positive photosensitive heat-resistant resin precursor composition, the effect is large because the amount of photosensitive component to be added is large.

The photosensitive heat-resistant resin precursor of the present invention is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The coating film thickness, the coating method, the solid content concentration of the composition,
Depending on the viscosity, etc., the film thickness after drying is usually 0.1
To 150 μm. Next, the substrate coated with the photosensitive heat-resistant resin precursor is dried to obtain a photosensitive heat-resistant resin precursor film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50 ° C to 150 ° C for 1 minute to several hours.

Next, the photosensitive heat-resistant resin precursor film is irradiated with actinic radiation and exposed. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm) and h-line (405 n) of a mercury lamp are used.
m) and g-line (436 nm) are preferably used.

Next, development is performed after exposure. N as a developer
-Methylpyrrolidone, N, N-dimethylacetamide,
In polar solvents such as dimethyl sulfoxide, methanol, ethanol, alcohols such as isopropanol, ethyl lactate, esters such as propylene glycol monomethyl ether acetate, hydrocarbons such as xylene,
Ketones such as cyclopentanone and cyclohexanone,
An alkaline aqueous solution such as an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of potassium hydroxide, or an aqueous solution of diethylaminoethanol, a mixture thereof, or a mixture obtained by adding a surfactant thereto can be used. After development
Rinse with water, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, ethyl lactate, etc.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 ° C. to 500 ° C. This imidization is carried out for 5 minutes to 5 hours while increasing the temperature stepwise, or selecting a certain temperature range and continuously increasing the temperature. As an example, 140 ° C,
Heat treatment is performed at 200 ° C. and 350 ° C. for 30 minutes each. Alternatively, a method of linearly raising the temperature to 400 ° C. over 2 hours may be used.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

<Measurement of Oxygen Concentration> Using an oxygen concentration meter LC-750L manufactured by Toray Engineering Co., Ltd., gas was introduced from the exhaust port of the oven to measure the oxygen concentration in the oven.

<Measurement of Mechanical Properties> A heat-resistant resin film formed on a 6-inch silicon wafer was treated with a solution of 45% hydrofluoric acid and 60% nitric acid at a volume ratio of 1: 3, and the periphery of the heat-resistant resin film was damaged. And soaked for 5 minutes. Thereby, the heat-resistant resin film was separated from the wafer. This heat-resistant resin film was cut into a strip having a width of 1 cm and a length of 8 cm so as not to damage the cut surface. Using this sample, Orientec TM-
100, the measurement length between chucks for measurement is 5c
The measurement was performed according to ASTM in m. At this time, the strength can be obtained by dividing the maximum load by the cross-sectional area of the film, and the elongation can be obtained by obtaining the breaking point. A problem arises when the elongation is less than 10% in this measurement.

Synthesis Example 1 In a 1-liter four-necked flask, 2,2 ′ was placed under a nitrogen stream.
-Bis (trifluoromethyl) benzidine 30.4g
(0.095 mol) and 1.2 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 150 g of N-methylpyrrolidone. To this, 29.4 g (0.1 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added and reacted at room temperature for 6 hours to obtain a polyamic acid (polyimide precursor). To this solution was added 30 g of nifedipine and 50 g of N-methylpyrrolidone, and the mixture was stirred at room temperature for 2 hours.
Varnish A, a photosensitive heat-resistant resin precursor, was obtained.

Synthesis Example 2 2,2-bis (3-amino-4-hydroxybenzene) hexafluoropropane (BAHF) under a stream of dry nitrogen
18.3 g (0.05 mol) was dissolved in 100 ml of N, N-dimethylacetamide and cooled to -5 ° C. Here, 26.4 g (0.3 mol) of glycidyl methyl ether was added, and 21.1 g of trimellitic anhydride chloride was added.
(0.1 mol) dissolved in 50 g of acetone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropping, the temperature of the solution was raised to 10 ° C., and stirring was continued for 1 hour, and then, the solution was stirred at 20 ° C. for 1 hour. Thereafter, 9.01 g (0.04 mol) of diaminodiphenyl ether and 2.5 g (0.01 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added, and the mixture was stirred at 20 ° C. for 6 hours. Continued. After completion of the stirring, the solution was poured into 10 l of water to obtain a precipitate of polyhydroxyamidamic acid. The precipitate was collected by filtration and then dried in a vacuum drier at 60 ° C. for 20 minutes.
Let dry for hours. This dried polyhydroxyamidamic acid (polyimide oxazole precursor) solid 10
g and 4 g of 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) as orthonaphthoquinonediazidesulfonic acid ester were dissolved in 20 g of gamma-butyrolactone to obtain varnish B as a photosensitive heat-resistant resin precursor.

Synthesis Example 3 Under dry nitrogen flow, 36.6 g (0.1 mol) of BAHF was dissolved in 150 ml of N, N-dimethylacetamide and cooled to -5 ° C. Here, 52.8 g (0.6 mol) of glycidyl methyl ether was added, and a solution obtained by dissolving 20.3 g (0.1 mol) of isophthalic acid chloride in 100 g of acetone did not exceed 0 ° C. Was dropped. After completion of the dropwise addition, the temperature of the solution was raised to 10 ° C., and stirring was continued for 1 hour, and thereafter, the solution was stirred at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a precipitate of polyhydroxyamidamic acid. The precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours.
10 g of this dried polyhydroxyamide (polybenzoxazole) solid and 2 g of 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) as orthonaphthoquinonediazide sulfonic acid ester are dissolved in 20 g of gamma-butyrolactone to obtain a photosensitive heat-resistant resin precursor. Of varnish C was obtained.

Synthesis Example 4 18.3 g (0.05 mol) of BAHF was added to ethanol 15
Dissolved in 0 ml and cooled to 5 ° C. Where potassium
11.2 g (0.1 mol) of t-butoxide were gradually added. Further, 21.8 g (0.1 mol) of t-butyl dicarbonate was gradually added, and stirring was continued for 2 hours to obtain a diamine compound in which the hydroxyl group of BAHF was protected by a t-butoxycarbonyl group. This solution was poured into 1 liter of water to obtain a precipitate. This precipitate was collected by filtration, and dried at 30 ° C. in a vacuum drier.
Dried for hours.

In a dry nitrogen stream, BAHF 27.5 g
(0.075 mol) and a diamine obtained by protecting the hydroxyl group of BAHF synthesized above with a t-butoxycarbonyl group.
4 g (0.025 mol) was dissolved in 150 ml of N, N-dimethylacetamide and cooled to -5 ° C. here,
52.8 g (0.6 mol) of glycidyl methyl ether was added, and a solution in which 20.3 g (0.1 mol) of isophthalic chloride was dissolved in 100 g of acetone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. did. After dropping, 1
The temperature of the solution was raised to 0 ° C., stirring was continued for 1 hour, and then, stirring was performed at 20 ° C. for 6 hours. After completion of the stirring, the solution was poured into 10 l of water to obtain a precipitate of polyhydroxyamidamic acid. The precipitate was collected by filtration and then dried in a vacuum dryer at 60 ° C. for 20 hours. 10 g of this dried polyhydroxyamide (polybenzoxazole) solid and NAI-105 (Midori Chemical Co., Ltd.) as a photoacid generator
1 g) was dissolved in 20 g of gamma-butyrolactone to obtain varnish D as a photosensitive heat-resistant resin precursor.

Synthesis Example 5 In a dry air stream, 10.9 g (0.05 mol) of pyromellitic anhydride was dissolved in 100 g of gamma-butyrolactone in a 500 ml four-necked flask. Here 12
g of 2-hydroxyethyl methacrylate (0.1 mol) and 7 g of pyridine were added and reacted at 50 ° C. for 1 hour. This solution was ice-cooled, and a solution of 21 g of dicyclohexylcarbodiimide (0.1 mol) dissolved in 25 g of gamma-butyrolactone was added dropwise over 15 minutes. Further, 10 g of 4,4′-diaminodiphenyl ether (0,0
(5 mol) in 25 g of gamma-butyrolactone was added dropwise over 10 minutes. This solution was reacted for 3 hours under ice cooling, and then reacted at 50 ° C. for 1 hour. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 3 liters of water to produce a polyamic acid ester precipitate. The precipitate was collected, washed with water and methanol, and then dried in a vacuum drier at 50 ° C. for 24 hours. 15 g of this polyamic acid ester powder and 0.75 g of mercaptobenzimidazole, 1 g of trimethylolpropane triacrylate, 2 g of ethylene glycol dimethacrylate, 0.03 g of p-tert-butylcatechol,
0.5 g of Michler's ketone, 0.5 g of 3-methacryloxypropyldimethoxysilane, 0.5 g of 1-phenyl-1,2-propanedione-2- (o-benzoyl)
Varnish E, a photosensitive heat-resistant resin precursor to which oxime was added, was obtained.

Synthesis Example 6 Under a nitrogen stream, 25.5 g of 3,5-diaminobenzoic acid-2-hydroxyethyl methacrylate ester (BEM-S, manufactured by Kawasaki Kaken) was placed in a 1-liter four-necked flask in a 4-neck flask.
95 mol) and 1.2 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane
-Methyl-2-pyrrolidone was dissolved in 100 g.
To this, 29.0 g (0.099 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added and reacted at room temperature for 6 hours to obtain a polyamic acid. N
-Phenyldiethanolamine 1.25 g, N-phenylglycine 1.25 g, ethylene glycol dimethacrylate 10 g, and varnish F as a photosensitive heat-resistant resin precursor
I got

Synthesis Example 7 In a 1-liter four-necked flask, 4,4'-
19.0 g (0.095 mol) of diaminodiphenyl ether and 1.2 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 100 g of N-methyl-2-pyrrolidone. . Here, 10.8 g (0.05 mol) of pyromellitic anhydride and 3,
15.0 g (0.047 mol) of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride was added and reacted at room temperature for 6 hours to obtain a polyamic acid. 13 g of glycidyl methacrylate was added thereto and reacted at room temperature for 12 hours. 5 g of ethylene glycol dimethacrylate and 2.5 g of N-phenylglycine, 0.2 g of 3,
3'-carbonylbis (7-diethylaminocoumarin)
Was added to obtain a varnish G of a photosensitive heat-resistant resin precursor.

Synthesis Example 8 In a nitrogen stream, 4,4'-
19.0 g of diaminodiphenyl ether (0.095
Mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.005 mol) with N-methyl-2
-Dissolved in 100 g of pyrrolidone. Here, 10.8 g (0.05 mol) of pyromellitic anhydride and 3,3 ', 4
4'-benzophenonetetracarboxylic dianhydride in 1
5.0 g (0.047 mol) was added and reacted at room temperature for 6 hours to obtain a polyamic acid. Here, 15 g of N-methylol methacrylamide, 5 g of ethylene glycol dimethacrylate and 2.5 g of N-phenylglycine, 0.2 g
Was added to obtain Varnish H, a photosensitive heat-resistant resin precursor.

Synthesis Example 9 In a nitrogen stream, 4,4'-
19.0 g of diaminodiphenyl ether (0.095
Mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (0.005 mol) with N-methyl-2
-Dissolved in 100 g of pyrrolidone. Here, 10.8 g (0.05 mol) of pyromellitic anhydride and 3,3 ', 4
4'-benzophenonetetracarboxylic dianhydride in 1
5.0 g (0.047 mol) was added and reacted at room temperature for 6 hours to obtain a polyamic acid. 33 g (0.18 mol) of N, N-diethylaminoethyl methacrylate, 10 g of diethylene glycol dimethacrylate were added to this solution.
And 1.25 g of N-phenyldiethanolamine and 1.25 g of N-phenylglycine were added to obtain Varnish I of a photosensitive heat-resistant resin precursor.

Examples 1 and 2 and Comparative Example 1 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the varnish A of the photosensitive heat-resistant resin precursor has a thickness of 10 μm after prebaking. Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 140 ° C
Pre-baking was performed to obtain a positive photosensitive heat-resistant resin precursor film. Next, it was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 2 minutes, and then immersed in water for 1 minute. After that, it was dried by blowing nitrogen. By the same method, a total of three samples were prepared. Inert Oven INH- made by Koyo Lindberg Co., Ltd.
After performing a heat treatment at 140 ° C. for 30 minutes in each of an oxygen concentration of 10 ppm (Example 1), an oxygen concentration of 100 ppm (Example 2), and air (Comparative Example 1), the temperature of 400 ° C.
The temperature was raised over 1 hour, and then left at 400 ° C. for 1 hour. When the temperature in the oven became 100 ° C. or less, the film was taken out and the mechanical properties of the film were measured. Oxygen concentration 10pp
m was 40% and the oxygen concentration of 100 ppm was 25%, whereas those heat-treated in air were significantly reduced to an elongation of 5% or less.

Examples 3 and 4, Comparative Example 2 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the film thickness after prebaking a varnish B of a photosensitive heat-resistant resin precursor is 10 μm. Developer S
Spin coating was performed using KW-636. Then, S
Using a hot plate of KW-636, 3
Pre-baking was performed to obtain a positive photosensitive heat-resistant resin precursor film. Next, it was immersed in a 0.6% tetramethylammonium hydroxide aqueous solution for 2 minutes, and then immersed in water for 1 minute. After that, it was dried by blowing nitrogen.
By the same method, a total of three samples were prepared. Inert oven INH-15 manufactured by Koyo Lindberg Co., Ltd.
After performing heat treatment at 140 ° C. for 30 minutes each in an oxygen concentration of 10 ppm (Example 3), an oxygen concentration of 100 ppm (Example 4), and air (Comparative Example 2), the temperature was raised to 350 ° C. over 1 hour. Temperature, then leave at 350 ° C for 1 hour,
The film was taken out when the temperature in the oven became 100 ° C. or less, and the mechanical properties of the film were measured. The sample with an oxygen concentration of 10 ppm is 50%, and the sample with an oxygen concentration of 100 ppm is 3%.
While the elongation was 5%, that of the one heat-treated in air was greatly reduced to 8%.

Examples 5 and 6, Comparative Example 3 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the film thickness after prebaking a varnish C of a photosensitive heat-resistant resin precursor is 10 μm. Developer S
Spin coating was performed using KW-636. Then, S
Using a hot plate of KW-636, 3
Pre-baking was performed to obtain a positive photosensitive heat-resistant resin precursor film. Next, it was immersed in a 1.2% aqueous solution of tetramethylammonium hydroxide for 2 minutes, and then immersed in water for 1 minute. After that, it was dried by blowing nitrogen.
By the same method, a total of three samples were prepared. Inert oven INH-15 manufactured by Koyo Lindberg Co., Ltd.
, Heat treatment was performed at 140 ° C. for 30 minutes each in an oxygen concentration of 10 ppm (Example 5), an oxygen concentration of 100 ppm (Example 6), and air (Comparative Example 3), and then the temperature was raised to 350 ° C. over 1 hour. Temperature, then leave at 350 ° C for 1 hour,
The film was taken out when the temperature in the oven became 100 ° C. or less, and the mechanical properties of the film were measured. 30% with an oxygen concentration of 10 ppm and 1% with an oxygen concentration of 100 ppm.
While the elongation was 8%, the one heat-treated in the air was greatly reduced to an elongation of 5% or less.

Examples 7 and 8 and Comparative Examples 4 to 64 Dainippon Screen Co., Ltd. was applied to a varnish D of a photosensitive heat-resistant resin precursor so that the film thickness after prebaking was 10 μm on a 4-inch silicon wafer. Coater Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 110 ° C
Pre-baking was performed to obtain a positive photosensitive heat-resistant resin precursor film. Next, it was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, and then immersed in water for 1 minute. After that, it was dried by blowing nitrogen. By the same method, a total of three samples were prepared. Inert Oven INH- made by Koyo Lindberg Co., Ltd.
After performing a heat treatment at 140 ° C. for 30 minutes each in an oxygen concentration of 10 ppm (Example 7), an oxygen concentration of 100 ppm (Example 8), and air (Comparative Example 4), the temperature of 350 ° C.
The temperature was raised over 1 hour, and then left at 350 ° C. for 1 hour. When the temperature in the oven became 100 ° C. or less, the film was taken out, and the mechanical properties of the film were measured. Oxygen concentration 10pp
m was 25% and the oxygen concentration of 100 ppm was 15%, whereas those heat-treated in air were significantly reduced to an elongation of 5% or less.

Examples 9 and 10 and Comparative Examples 5 to 74 Dainippon Screen Co., Ltd. was applied to a varnish E of a photosensitive heat-resistant resin precursor so that the film thickness after prebaking was 10 μm on a 4-inch silicon wafer. Coater Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 100 ° C
By pre-baking, a negative photosensitive heat-resistant resin precursor film was obtained. Next, the mask was not set in an exposure machine (PLA-501 manufactured by Canon Inc.),
Exposure was performed at 0 mJ / cm ² (intensity measured at 405 nm). Development is SKW-636 manufactured by Dainippon Screen Mfg.
Was sprayed at 1,000 rpm for 30 seconds. Thereafter, ethyl lactate was sprayed at 1,000 rotations for 5 seconds for rinsing treatment, and the mixture was shaken off at 3000 rotations for 8 seconds and dried. By the same method, a total of three samples were prepared. Using an inert oven INH-15 manufactured by Koyo Lindberg Co., Ltd., an oxygen concentration of 10 ppm (Example 9), an oxygen concentration of 30 ppm (Example 10), and an oxygen concentration of 1
50 ppm (Comparative Example 5), oxygen concentration 1% (Comparative Example 6),
Heat treatment at 140 ° C. in air (Comparative Example 7) for 30
After heating for 1 minute, the temperature was raised to 400 ° C. over 1 hour, then left at 400 ° C. for 1 hour, and then cooled to room temperature in an oven. When the mechanical properties of these films were measured, an oxygen concentration of 10
ppm has an elongation of 20% and an oxygen concentration of 30 ppm
The sample having an oxygen concentration of 150 ppm had an elongation of 7%. When the film was heat-treated in air with an oxygen concentration of 1%, the film was brittle and the mechanical properties could not be measured.

Examples 11 and 12 and Comparative Example 8 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the film thickness after prebaking a varnish F of a photosensitive heat-resistant resin precursor was 10 μm. Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 100 ° C
By pre-baking, a negative photosensitive heat-resistant resin precursor film was obtained. Next, the mask was not set in an exposure machine (PLA-501 manufactured by Canon Inc.),
Exposure was performed at 0 mJ / cm ² (intensity measured at 405 nm). Development is SKW-636 manufactured by Dainippon Screen Mfg.
Was sprayed at 1,000 rpm for 30 seconds. Thereafter, ethyl lactate was sprayed at 1,000 rotations for 5 seconds for rinsing treatment, and the mixture was shaken off at 3000 rotations for 8 seconds and dried. By the same method, a total of three samples were prepared. The obtained exposed and developed wafer was subjected to an oxygen concentration of 10 ppm (Example 11) and an oxygen concentration of 10 using an inert oven INH-15 manufactured by Koyo Lindberg Co., Ltd.
After performing a heat treatment at 140 ° C. for 30 minutes at 0 ppm (Example 12) and an oxygen concentration of 1% (Comparative Example 8), 380 ° C.
, The temperature was raised over 1 hour, then left at 380 ° C. for 1 hour, and then cooled to room temperature in an oven. When the mechanical properties of these films were measured, those with an oxygen concentration of 10 ppm
%, And 15% with an oxygen concentration of 100 ppm, but the film that had been heat-treated at an oxygen concentration of 1% was brittle and the mechanical properties could not be measured.

Examples 13 and 14, Comparative Example 9 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the film thickness after prebaking a varnish G of a photosensitive heat-resistant resin precursor was 10 μm. Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 100 ° C
By pre-baking, a negative photosensitive heat-resistant resin precursor film was obtained. Next, the mask was not set in an exposure machine (PLA-501 manufactured by Canon Inc.),
Exposure was performed at 0 mJ / cm ² (intensity measured at 405 nm). Immediately before the development, a heat treatment at 80 ° C. for 1 minute was performed using a hot plate (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Development is SKW- manufactured by Dainippon Screen Mfg.
Using a developing device of No. 636, N-methyl-2
-A developer of 10: 3 by volume ratio of pyrrolidone and xylene was sprayed for 3 seconds. After this, it is stopped for 60 seconds, and then 100 seconds.
Rinse treatment by spraying the developer at 0 rotation for 5 seconds and spraying isopropyl alcohol at 1000 rotations for 5 seconds.
Shake off for 8 seconds and spin dry. By the same method, a total of three samples were prepared. The obtained exposed and developed wafer is transferred to an inert oven IN by Koyo Lindberg Co., Ltd.
Using H-15, an oxygen concentration of 10 ppm (Example 1)
3) After heat treatment at 140 ° C. for 30 minutes at an oxygen concentration of 100 ppm (Example 14) and an oxygen concentration of 1% (Comparative Example 9), the temperature was raised to 380 ° C. over 1 hour.
After leaving at 80 ° C. for 1 hour, it was cooled in an oven to room temperature.
When the mechanical properties of these films were measured, the oxygen concentration was 10 pp.
In the case of m, the elongation was 20%. In the case of an oxygen concentration of 100 ppm, the elongation was 12%. In the case of an oxygen concentration of 150 ppm, the elongation was 7%. Mechanical properties could not be measured.

Examples 15 and 16 and Comparative Example 10 A coater manufactured by Dainippon Screen Co., Ltd. was coated on a 4-inch silicon wafer so that the varnish H of the photosensitive heat-resistant resin precursor had a thickness of 10 μm after prebaking. Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 100 ° C
By pre-baking, a negative photosensitive heat-resistant resin precursor film was obtained. Next, the mask was not set in an exposure machine (PLA-501 manufactured by Canon Inc.),
Exposure was performed at 0 mJ / cm ² (intensity measured at 405 nm). Immediately before the development, a heat treatment at 80 ° C. for 1 minute was performed using a hot plate (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Development is SKW- manufactured by Dainippon Screen Mfg.
Using a developing device of No. 636, N-methyl-2
-A developer of 10: 3 by volume ratio of pyrrolidone and xylene was sprayed for 3 seconds. After this, it is stopped for 60 seconds, and then 100 seconds.
Rinse treatment by spraying the developer at 0 rotation for 5 seconds and spraying isopropyl alcohol at 1000 rotations for 5 seconds.
Shake off for 8 seconds and spin dry. By the same method, a total of three samples were prepared. The obtained exposed and developed wafer is transferred to an inert oven IN by Koyo Lindberg Co., Ltd.
Using H-15, an oxygen concentration of 10 ppm (Example 1)
3) After heat treatment at 140 ° C. for 30 minutes at an oxygen concentration of 100 ppm (Example 14) and an oxygen concentration of 1% (Comparative Example 9), the temperature was raised to 380 ° C. over 1 hour, and then 3
After leaving at 80 ° C. for 1 hour, it was cooled in an oven to room temperature.
When the mechanical properties of these films were measured, the oxygen concentration was 10 pp.
In the case of m, the elongation was 25%, in the case of 100 ppm oxygen concentration was 15%, in the case of 150 ppm oxygen concentration, the elongation was 7%, and when heat-treated at an oxygen concentration of 1%, the film was brittle. Mechanical properties could not be measured.

Examples 17 and 18 and Comparative Example 11 A coater manufactured by Dainippon Screen Co., Ltd. on a 4-inch silicon wafer so that the film thickness after prebaking a varnish H of a photosensitive heat-resistant resin precursor was 10 μm. Developer S
Spin coating was performed using KW-636. Then, S
Using a KW-636 hot plate at 100 ° C
By pre-baking, a negative photosensitive heat-resistant resin precursor film was obtained. Next, the mask was not set in an exposure machine (PLA-501 manufactured by Canon Inc.),
Exposure was performed at 0 mJ / cm ² (intensity measured at 405 nm). Immediately before the development, a heat treatment at 80 ° C. for 1 minute was performed using a hot plate (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Development is SKW- manufactured by Dainippon Screen Mfg.
The developer DV-3 was rotated at 100 rotations using the developing device No. 636.
08 (Toray) was sprayed for 3 seconds. Thereafter, the apparatus is stopped for 60 seconds, and then sprayed with a developer at 1000 rotations for 5 seconds.
Rinsing treatment was performed by spraying isopropyl alcohol at 0 rotation for 5 seconds, and shake-drying was performed at 3000 rotations for 8 seconds. By the same method, a total of three samples were prepared. The exposed and developed wafer thus obtained was subjected to an oxygen concentration of 10 pp using an inert oven INH-15 manufactured by Koyo Lindberg Co., Ltd.
m (Example 15), oxygen concentration 100 ppm (Example 1)
6) After performing heat treatment at 140 ° C. for 30 minutes in air (Comparative Example 10), the temperature was raised to 350 ° C. over 1 hour, then left at 350 ° C. for 1 hour, and then cooled in an oven to room temperature. When the mechanical properties of these films were measured, those having an oxygen concentration of 10 ppm had an elongation of 60% and an oxygen concentration of 1%.
The one with 00 ppm was 40%, but the one which was heat-treated in the air had a large drop in elongation of 8%.

[0034]

According to the present invention, a polyimide film having improved mechanical properties such as elongation can be obtained.

Claims (3)

[Claims] 1. A method for heat-treating a photosensitive heat-resistant resin precursor, comprising exposing and developing the photosensitive heat-resistant resin precursor composition and then heat-treating the composition in an atmosphere having an oxygen concentration of 100 ppm or less. 2. The method for heat treating a photosensitive heat-resistant resin precursor according to claim 1, wherein the heat treatment is performed in an atmosphere having an oxygen concentration of 20 ppm or less. 3. The heat treatment method for a photosensitive heat-resistant resin precursor according to claim 1, wherein the photosensitive heat-resistant resin precursor is a positive type.