JPH03259148A - Photosensitive agent, photosensitive heat-resistant material, and resin-sealed semiconductor device - Google Patents

Abstract

PURPOSE:To obtain a photosensitive agent superior in sensitivity to the g-line and adhesion to a substrate, capable of forming a fine pattern, and useful as a photoresist by using the photosensitive agent specified in structure. CONSTITUTION:The photosensitive agent is represented by formula I in which A is a divalent organic group, and D is represented by formula II, III, or the like. These naphthoquinonediazido derivatives composing the photosensitive agent are novel compounds high in sensitivity in the longer wavelength region and favorably used for the photoresist and the photosensitive heat resistant material, thus permitting the obtained photoresist to form a fine pattern with a small amount of exposure, and the photosensitive heat-resistant material to be superior in photosensitivity and to be formed into a sharp pattern, and enhanced in adhesion to the semiconductor substrate and sealing resin.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention provides a photosensitizer comprising a naphthoquinonediazide sulfonic acid derivative, a photosensitive heat-resistant material containing this photosensitizer, and a photosensitive heat-resistant material containing this photosensitizer. The present invention relates to a resin-sealed semiconductor device used as a protective film.

(Prior Art) In the semiconductor field, circuits for integrated circuits and printed wiring boards are created by microlithography using photoresist compositions. Generally, the microlithography method consists of the following steps. When making integrated circuits, a photoresist composition is applied to the surface of a silicon wafer. Additionally, when creating a printed circuit on a printed circuit board, a photoresist composition is applied onto a substrate material such as aluminum, copper, gold, or indium/tin oxide. Next, the coating film of the photoresist composition is dried to fix the photoresist onto the substrate. Thereafter, the photoresist is exposed through a mask, and exposed or unexposed areas are treated with a developer.

There are two types of photoresist compositions: negative type and positive type. In the case of a positive photoresist composition, the exposed areas are dissolved in a developer and removed, and the unexposed areas remain insoluble in the developer, so that a positive image (pattern) is formed.

Thereafter, an etching process is performed using the photoresist pattern as a mask.

Incidentally, it is known that positive photoresists are advantageous in forming fine patterns. Conventionally, naphthoquinone diazide compounds have been commonly used as components of positive photoresists. As these naphthoquinonediazide compounds, the following are known, for example.

(Conventional Example 1) (Conventional Example 2) However, when these naphthoquinone diazide compounds are used, there is a problem that the exposure sensitivity is low to the g-line (4.36 nm) of a mercury lamp. Furthermore, photoresists containing these compounds tend to have poor adhesion to the substrate. Therefore, there is a need for a new photosensitizer that does not have these drawbacks.

Furthermore, since elements formed on a semiconductor substrate are easily affected by the external environment, a protection mechanism is provided to maintain reliability. As this protective film, inorganic materials such as silicon dioxide, silicon nitride, and alumina are used. A conventional resin-sealed semiconductor device has a structure in which a protective film made of the above-mentioned inorganic material is formed on a semiconductor substrate, and the device is further sealed with an epoxy resin composition or the like. but,
Encapsulation resins such as epoxy resins have the property of permeating moisture, and as the element pellet becomes larger, cracks tend to occur in the protective film due to the difference in thermal expansion coefficient between the encapsulant resin and the semiconductor substrate. Corrosion of wiring patterns made of aluminum or the like has been observed due to the intrusion of moisture.

As a countermeasure, a polyimide protective film is further formed on the protective film made of the inorganic material. Polyimide resins have become widely used in recent years because they can be formed into a film through a simple process and can be stabilized at relatively low temperatures. However, in these applications, it is usually necessary to form holes in the polyimide protective film by performing pattern processing such as through holes or pad processing for establishing conduction with external leads. This processing step requires the use of a photoresist, which has the drawback of requiring a complicated process and a long time to form the protective film.

On the other hand, JP-A-49-115541 discloses a photosensitive material and a compound having a repeating unit represented by the following formula in 17. However, this material has the disadvantage that the synthesis process of a tetrafunctional compound having a photosensitive group or the synthesis process of a polyamic acid is complicated.

Further, Japanese Patent Publication No. 59-52822 describes a heat-resistant photosensitive material containing a compound containing a carbon-carbon double bond and an amino group that can be converted into 211 or polymerized by electromagnetic waves. [5 However, this material has a problem of poor adhesion to the semiconductor substrate or the sealing resin, impairing the reliability of the semiconductor device.

The aforementioned materials have negative photosensitive properties.

On the other hand, as a positive photosensitive heat-resistant material, JP-A-82-I,
45240 proposes a polymer having an isoimide structure. However, 2. this material has low heat resistance;
This eliminates the drawbacks (such as low exposure sensitivity).

It was.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems. That is, the object is to provide a photosensitizer that has excellent exposure sensitivity to g-rays, is capable of forming fine patterns, has excellent adhesion to a substrate, and is useful as a photosensitive material. Another object of the present invention is to provide a photosensitive heat-resistant material that can form a sharp relief pattern without using a photoresist, has excellent adhesion to a semiconductor substrate and a sealing resin, and provides a protective film with excellent moisture resistance. With the goal. Furthermore, it is an object of the present invention to provide a highly reliable resin-capped conductor device using such an excellent protective film.

[Components of the invention (1st step to solving the problem) The photosensitizer of the present invention has the following formula (1)% formula% (1) (In the formula, A represents a divalent organic group, D is (In the formula, R is ) It is characterized by the following.

Among these, in the following general formula (IA) or (IB) 5, X is a direct bond, -0- CH2 5O2 C○- HOCH3CF, ○HIll
l l 1-N-C-, -C
-, -〇-, or -CHCo-CH3CF.

represents. ] represents. Furthermore, the hydrogen atom of the aromatic nucleus may be substituted with an alkyl group, a halogen atom, or a hydroxyl group. ) 1,2-naphthoquinone-2-diazide-4 (
or 5) -amide ester compounds of sulfonic acid are desirable.

The photosensitive heat-resistant material of the present invention has (a) the following general formula () (wherein, Z represents a tetravalent organic group having at least two carbon atoms, and Y represents a divalent organic group having at least one hydroxyl group). (representing an organic group) and a polyimide having a repeating unit represented by (b
)! It is characterized by containing the photosensitizer described in claim (1).

The resin-sealed semiconductor device of the present invention is characterized in that the surface of a semiconductor substrate on which elements are formed is coated with the photosensitive heat-resistant material as a protective film, and further sealed with a molding material resin.

The present invention will be explained in more detail below.

The amide ester compound of naphthoquinonediazide sulfonic acid or quinonediazide sulfonic acid, which is a photosensitizer of the present invention, is composed of naphthoquinonediazide sulfonic acid halide or quinonediazide sulfonic acid halide and the following general formula (II [
) is obtained by reacting with an aromatic aminophenol compound H2N-R-OH(DI) (wherein R is defined as above).

Specific examples of aromatic aminophenol compounds include p-
Aminophenol, ■-aminophenol, 3-aminophenyl-4°-hydroxyphenyl ether, 4-aminophenyl-4-hydroxyphenyl ether, 3-
Aminophenyl-4"-hydroxyphenylmethane, 4
-aminophenyl-4'-hydroxyphenylmethane,
2-(3-aminophenyl)-2-(4"-hydroxyphenyl)propane, 2-(4-aminophenyl)-2
-(4°-hydroxyphenyl)propane, 2-(3-
aminophenyl)-2-(4”-hydroxyphenyl)
Hexafluoropropane, 2-(4-aminophenyl)-
2-(4'-hydroxyphenyl)hexafluoropropane, 3-hydroxyphenyl-4"-aminophenyl ether, 2-(3-hydroxyphenyl)-2-(4°
-aminophenyl)propane, 2-(3-hydroquinphenyl)-2-(4-aminophenyl)hexafluoropronoprono, and the like. In addition to these aromatic aminophenol compounds, 3-aminophenyl-3
'-Hydroxyphenylmethane, 3-aminophenyl-
3-hydroxyphenyl ether, 2-(3-aminophenyl)-2-(3'-hydroxyphenyl)propane, etc. can also be used.

This synthetic reaction is usually carried out in an organic solvent.

Specific examples of organic solvents used in this case include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, cellosolve, methyl cellosolve, cyclohexanone, ethylene chloride, chloroform, acetonitrol, methyl acetate, ethyl acetate, butyl acetate, cellosolve acetate, dimethylformamide, N -Methyl-2-pyrrolidone and the like. Since hydrogen halide is produced as a by-product in this reaction, it is desirable to use alkali metal carbonates, alkali metal bicarbonates, organic amines such as triethylamine and pyridine, ethylene oxide, propylene oxide, etc. in combination to capture this. .

This reaction is preferably carried out at 0 to 100° C. for 1 to 50 hours in a place such as a yellow room shielded from ultraviolet rays.

The amide ester compound produced by this reaction is obtained from the reaction mixture by normal means, preferably by extraction using a mixed solvent of water and a poor solvent for water such as ethylene chloride, and then drying. Ru.

Specific examples of the photosensitizer according to the present invention are illustrated below.

(i-6) (knee 3> (knee 7>(I-4> , Z represents a tetravalent organic group having at least 2 carbon atoms) and a tetracarboxylic dianhydride represented by the following formula % formula % (wherein, Y represents a divalent organic group having at least one hydroxyl group) (representing an organic group).

For example, pyromellitic dianhydride, 3.3'
, 4.4-benzophenonetetracarboxylic dianhydride,
2,3.3',4'-benzophenonetetracarboxylic dianhydride, 3.3',4.4"-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride , 2.2-bis(3',4'-dicarboxyphenyl)prop'-dianhydride, 2.2-bis(
3", 4°-dicarboxyphenyl) hegisa" 70 lobrovanni anhydride, bis(3,4-dicarboxyphenyl)sulfonic anhydride, bis(3,4-dicarboxyphenyl)dimethylsilanianhydride, Bis(3,4dicarboxyphenyl)tetramethyldisiloxane dianhydride, 1
．． 4,5.8-naphthalenetetracarboxylic dianhydride,
Examples include 2,3.8.7-naphthalenetetracarboxylic dianhydride and butanetetracarboxylic dianhydride.

Regarding tetracarboxylic dianhydride, the following 1. One or more selected from the group of ``-4'' may be used.

Examples of diamines having at least one hydroxyl group that form the middle structure of polyimide include 3.3 dihydroxy-
4,4-one aminobifunyl, 3.3 diamino-4,
4'-dihydroxybiphenyl, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 2-(3 -Hydofukishi 4-
aminophenyl)-2-(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3-dihydroxy-4,4-diaminodiphenylsulfone, 3.3'-
Diamino-4,4'-dihydroxydiphenylsulfone, 3,3''-dihydroxy-4,4-diaminobenzophenone, 3,3'-diamino-4,4-dihydroxybenzophenone, 3,3°-dihydroxy-4,4' -diaminodiphenyl ether, 3.3°-diamino-4,
4"-dihydroxydiphenyl ether, 3.3dihydroxy-4,4-diaminodiphenylmethane, 2.6-
Diaminophenol, 2,4-diaminophenol, 3
．． 5-diaminophenol, 3-hydroxy-4゜4゛-diaminobiphenyl, 4-hydroxy-3,3°-diaminobiphenyl, 2-(3-amino-4-hydroxyphenyl)-2-(3-aminophenyl) Examples include hexafluoropropane, 3-hydroxy-4,4'-diaminodiphenyl sulfone, 3-hydroxy-4,4'-diaminodiphenyl ether, and 3-hydroxy-4,4'-diaminodiphenylmethane.

As the diamine, one or two selected from the above group
More than just species are used.

Furthermore, in the present invention, it is also possible to use together the diamine containing the aforementioned hydroxyl group and the diamine not containing the hydroxyl group shown below. In this case, it is desirable that the amount of diamine not containing a hydroxyl group to be used is 50 mol 96 or less of the total diamine. Specific examples of these diamines that do not contain a hydroxyl group include phenylenediamine, p-phenylenediamine, 2.4-hlylenediamine, 3.3'
-diaminodiphenyl ether, 4.4"-diaminodiphenyl ether, 3.4°-diaminodiphenyl ether, 3.3'-diaminodiphenyl sulfone, 4,4
“-diaminodiphenylsulfone, 3,4°-diaminodiphenylsulfone, 3,3°-diaminodiphenylmethane, 4.4°-diaminodiphenylmethane, 3.4'
-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4°-
Diaminodiphenylketone, 2.2°-bis(p-aminophenyl)propane, 2.2′-bis(p-aminophenyl)hexafluoropropane, l,3-bis(III
-aminophenoxy)benzene, 1,3-bis(p-aminophenoxy)benzene, 1,4-bis(p-aminophenoxy)benzene, 4-methyl-2,4-bis(p-aminophenoxy)benzene,
-aminophenyl)-1-pentene, 4-methyl-2,
4-bis(p-aminophenyl)-2-pentene, 1.
4-bis(α,α-dimethyl-p-aminobenzyl)benzene, imino-di-roof unilene diamine, 1.5
-diaminonaphthalene, 2,6-diaminonaphthalene,
4-methyl-2,4-bis(p-aminophenyl)pentane, 5(or 6)-amino-1-(p-aminophenyl)-1,3,3-trimethylindane, bis(p-aminophenyl) Phosphine oxyto, 4°4°-diaminoazobenzene, 4,4°-diaminodiphenylurea,
4.4'-bis(p-aminophenoxy)biphenyl,
2,2-bis[p-(p-aminophenoxy)phenyl]propane, 2,2-bis[p-(m-aminophenoxy)phenyl]benzophenone, 4,4°-bis(p-
aminophenoxy) diphenylsulfone, 4゜4'-bis[p-(α,α-dimethyl-p゛-aminobenzyl)
phenoxy]benzophenone, 4,4'-bis[p-(
α,α-dimethyl-p-aminobenzyl)phenoxy]
Aromatic diamines such as diphenylsulfone, bis(4-aminophenyl)dimethylsilane, and bis(4-aminophenyl)tetramethyldisiloxane are mentioned. Note that the hydrogen atom of the aromatic nucleus of these aromatic diamines is substituted with at least one substituent selected from the group of chlorine atom, fluorine atom, bromine atom, methyl group, methoxy group, cyano group, phenyl group, etc. It may also be a compound that has been

In addition to the aromatic diamines mentioned above, examples of diamines that do not contain hydroxyl groups include dimethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, Methylenediamine, 12-bis(3″-aminopropoxy)ethane, H2N-(CH2)3-0- (CH2)2-0
- (CH2) 3-Nl2.1.3-diaminocyclohexane, 1.4-diaminocyclohexane, 1.3-
Bisaminomethylcyclohexane, j,4-bisaminomethyl〉Chlohexane, 4,4-Schif'minodinechlorohequinlemethane, 4,4-diaminoxy; .6
-diamitsviridine, 2.6-diamino-8-triazine, bis(γ-amino, nopropyl)tetramethyldisylogyzan, 1,4-bis(γ-aminobrovirine methylsilyl)benzene, bis(4-amino Examples include butyl)tetramethyldisilogen, dibe(γ-aminopropyl)tetraphenyldisilone, and the like.

In the present invention, polyimide is synthesized as follows. First, in the first step, polyimide is formed by polycondensation reaction between tetracarboxylic dianhydride and a diamine containing at least one hydroxyl group (and if necessary, a diamine containing no hydroxyl group) in an organic solvent. Synthesize polyamic acid, which is a precursor of polyamic acid. The organic solvents used at this time include, for example, N,hl-dimethylacetamide, N,N-dimethylacetamide, L-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, γ-butyrolactre, sulborani, L~, Examples include j~l'+N'-radramedel urea, hexamethylphosboramide, tetrahydrogen chloride, dioxicani, and so on.

In the second reaction (C), the molar ratio of diamine to tetracarboxylic dianhydride is desirably in the range of 0.9 to 11:1. The reaction conditions are - boat fishing, reaction temperature -20 ~
- 100°C, reaction time ranges from 10 minutes to 20:10j.

From the polyamic acid obtained under the above-mentioned conditions, polyamic acid can be synthesized, for example, by the following method.
You can do something like that.

■7 sets of functional alkalis such as trutylamine.

In F, polyamic acid is dehydrated and cyclized using an acid anhydride such as acetic anhydride to form polyimide.

(2) In the presence of methylsulfonic acid, polyamic acid is dehydrated and cyclized using ff phosphorus oxide or polyphosphoric acid to form polyimide.

■Images such as benzene, toluene, xylene, and chlorobenzene that are azeotropic with water are added to the synthesized polyamic acid solution.
A solvent is added, and at a temperature above the azeotropic point of these organic solvents, the water produced by i+J is distilled out of the system, and the polyamic acid is dehydrated and cyclized to form polyimide.

The synthetic force method for polyimide is not limited to these methods.

In the photosensitive heat-resistant material of the present invention, the amount of the photosensitizer used is 0.1 to 5[) heavy El based on the polyimide resin.
% range is desirable. The weight of the photosensitive agent is 0.1 weight; if it is less than 0 weight, the exposure sensitivity of the photosensitive heat-resistant material decreases. Photosensitizer or 503Tif? %, there is a tendency for the performance as a membrane to be impaired. It is more desirable that the amount of photosensitizer used is in the range of 1 to 30 times R9b based on the polyimide resin.

The photosensitive heat-resistant material of the present invention is prepared in 12 as follows. For example, after synthesizing polyimide 11 using the method described above, the concentration of the polyimide resin in the reaction solution is adjusted using a white organic solvent 1, and a predetermined amount of photosensitizer is blended to prepare a uniform solution. Alternatively, the reaction solution may be mixed with methanol, ethanol, tanol,
The polyimide resin is injected into a poor solvent such as water to precipitate it as a solid, which is separated, obtained and dried, and then a predetermined amount of the polyimide resin and a predetermined amount of the photosensitizer are mixed in an organic solvent. Prepare a homogeneous solution by dissolving it in

Examples of organic solvents used in this case include tetrahydrofuran, dioxane, N,N-; It will be done. Also,
Along with these organic solvents, cellosolve, methyl cellosolve, butyl acetate, ethyl acetate, ethyl 1/nguri: 1-
It is also possible to use combinations of dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like.

If necessary, a modifier such as a silane coupling agent or a surfactant may be added to the photosensitive heat-resistant material of the present invention.

A relief pattern of a polyimide compound can be formed from the photosensitive heat-resistant material of the present invention in the following manner. That is, a solution (varnish) of a photosensitive heat-resistant material adjusted to an appropriate viscosity is applied onto a substrate using a spinner or the like, and the solution is dried preferably at a temperature of 100° C. or lower to remove the solvent. After drying, place a photomask on the coating film,
Irradiates electromagnetic waves such as ultraviolet rays, visible light, electron beams, and X-rays.

Next, by washing away the exposed areas with a developer, a polyimide relief pattern can be obtained.

The developing solution used at this time includes a quaternary ammonium salt solution such as a tetramethylammonium hydroxide aqueous solution, a trimethylhydroxyethylammonium hydroxide aqueous solution (for example, Tama Chemical's product name Corin TM-3); sodium hydroxide, hydroxide, etc. Examples include aqueous solutions of alkaline compounds such as potassium and sodium carbonate.

Thereafter, the relief pattern is heat-treated at 100 to 400°C, preferably at 250°C or higher, to obtain a relief pattern made of a polyimide film with excellent heat resistance and adhesion.

The resin-sealed semiconductor device of the present invention is manufactured by the following method. That is, a solution of the photosensitive heat-resistant material prepared as described above is applied to the surface of a semiconductor substrate on which an element is formed, the solvent is removed by heating, and a relief pattern is formed by exposure and development. After being cured by heat treatment to form a polyimide protective film, steps such as bonding are performed, and the polyimide is further sealed with a sealing resin to manufacture a resin-sealed semiconductor device.

The sealing resin used in the present invention is not particularly limited, and any known epoxy resin composition can be used. In addition, in order to reduce the stress of the epoxy sealing resin cured with phenol novolac resin, we have also developed a siloxane-modified phenol novolac epoxy resin (Japanese Patent Laid-Open No. 58-2141
Modified epoxy resin compositions such as alkylphenol-modified phenol novolac epoxy resin (Japanese Patent Application Laid-Open No. 59-30820) may also be used.

The most common method for this sealing is low-pressure transfer molding, but injection molding, compression molding,
Sealing by casting or the like is also possible.

Note that during these moldings, it is desirable that the curing temperature of the epoxy resin be 150° C. or higher. Further, if necessary, post-curing may be performed at a temperature of 160 to 190°C for 2 to 24 hours.

The resin-sealed semiconductor device of the present invention is 5in2, PSG
(phosphosilicate glass), SiN, and other passivation films, and also has extremely good adhesion to epoxy sealing resins, is used as a protective film, so moisture cannot enter from the interface. This effectively prevents corrosion of metals such as aluminum forming LSI circuits, resulting in a significant improvement in the reliability of LSIs.

(Example) Hereinafter, the present invention will be explained in more detail based on examples.

Example 1 (Photosensitizer) (a) 1. ．． 2-naphthoquinone-2-diazide-5-
Sulfonic acid 2-(4-aminophenyl)-2-(4-
Synthesis of hydroxyphenyl)propanamide ester 1,2-naphthoquinone-2-diazide-
26.36 g (0.1 mol) of 5-sulfonic acid chloride
, 11.3 g (0.05 mol) of 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane and 400 ml of 1,4-dioxane were added, and while stirring the mixture thoroughly, sodium carbonate was added. 15g in 150m of water
1 was gradually added. This mixture was then stirred at room temperature for 15 hours.

The reaction mixture was poured into 1.000 ml of water containing 10 ml of hydrochloric acid, producing a yellow precipitate. After standing for a while and discharging the supernatant by decantation, 700 ml of methylene chloride and 200 ml of water were added to the reaction mixture.
The precipitate was dissolved in methylene chloride to extract the product.

The methylene chloride phase was washed three times with a 1% aqueous sodium carbonate solution, twice with 250 ml of water, and twice with saturated brine, dried over anhydrous sodium sulfate, and then filtered. The methylene chloride solution was evaporated to dryness and dried under reduced pressure to give a yellowish brown precipitate 2.
6.9g was obtained. Product yield was 79%.

The IR spectrum of this product is shown in Figure 1, and the elemental analysis values are shown in Table 1 (Figure 4).

Table 1 Elemental analysis value (%) CM NS Theoretical value 61. ．． 7 2,2 10.3 9.4 Analysis value 80.9 2.1 9.7 9.7 The melting point of the second product is 137-140°C QA1 1/2.

According to the U■ spectrum, this month, the acid had a large absorption at 399ni+.

From these prefectures, this product is 1.2~naphtogyno]
・~2-diazide 5~sulfo5・acid 2-(4-7
It was confirmed that the product was ester of 2-(4-nophenyl)-propanamide.

(1)) Photosensitivity test Using the photosensitizer of Example 1, a fine solid was prepared as follows.
Attempts were made to form a Cresol, noholac resin (molecular weight 30,000, polystyrene equivalent) 10g and 2-(
4-aminofuconyl)-2-(4-hydro)゛-shi゛2
Dissolve 2.5 g of amidogostyl (phenyl)probeni and amidogostyl in 40 g of ethyl celloprobenacetate.15, pore size 0.
A solution of the C photosensitive bamboo composition was prepared by filtering it through a 5" filter. This solution was dried on a hot plate at 9Ω°C for 2D minutes to obtain a coated film with a thickness of 2.5 yen. A test pattern mask was brought into close contact with this coating 4, h, and ultraviolet rays were irradiated at an exposure dose of 5 mJ/'cy+ti2. Then, tetramethylammo m:, umhydrogishi 2,0
When developed at 25° C. for 60 seconds using a wt % aqueous solution, it was possible to obtain a stamp with a line width of 1 on.

Comparative Example 1 (Photosensitizer) In place of 2.5 g of the photosensitizer in Example], 3.4-dihydroxybensif, 1-, non-1,2-naphtho-4, non-di"aziF" 5-sulfonic acid diester Using 2.5 g, formation of a C fine pattern was attempted in the same manner as in Example 1.

As a result, it was observed that the pattern that should originally have a line width of I.01 had a line width of 0.7 ur*, and that the contrast between the exposed and unexposed areas was poor.

Examples 2 to 7 (Photosensitive and heat resistant 100%) (a) Synthesis of polyimide resin Synthesis example 1 (Synthesis of poly1'E resin A) Remove the stirring bar, thermometer, and dropping funnel. inside the flask,
3. : 3°, 4.4-Benicif J)-tetracarboxylic dianhydride IB, 110 g (0.05 mol) Pyromellitic acid dianhydride 10.90 [i g (0.05 mol) and 100 g of N-methyl-2-pyro 11 tons were charged, thoroughly stirred, and cooled to 0°C. This suspension was kept at 0°C and 2,2-bis(3-amino-4-hydroxyphenyl)hexafuror'I propane
95g (0,095+l) and bis(γ-amitubr)
``J Bill) Tetramesaldisilok4kun 1.243g
(0,00!5'El) to 150g of N-methyl-2-10ridone! , 1m dissolution [1. The solution was gradually added dropwise from the dropping funnel. After completion of the dropwise addition, stirring was continued for 6 hours at a temperature of 0 to 10 to synthesize polyamic acid. 200m of goldenrod in this solution! was added, heated using an oil bath, and heated at high speed for 5.2 hours.12. After that, K/L was distilled off along with by-produced water. After cooling this solution to room temperature, methanol,
A precipitate of polyimide was obtained.

This precipitate was filtered off and dried under reduced pressure of 80'l"'. This is called polyimide resin A.

Synthesis Example 2 (Synthesis of Polyimide Resin B) 3.3',4.4-benzophenonetetracarboxylic dianhydride 32.22g (0.10 mol), 3.3'-
Dihydroxy-4,4”-diaminobinoenyl (0,
07 mol), 4,4-diaminosif J-nyl ether 5
．． 205g (0,028 mol), bis(γ-aminopropyl)tetramethyldisiloxane 0,994g (
0,004 mol), and N-methyl-2-pyrrolidone 2
Using 10 g, polyamic acid was synthesized in the same manner as in Synthesis Example 1. 6 g of triethylamine and 23 g of acetic anhydride were added to this solution, and the mixture was stirred for 7 hours at a solution temperature of 30°C.
Ta. This solution was treated in the same manner as in Synthesis Example] to obtain polyimide. This is called polyimide resin B.

(b): Preparation of photosensitive heat-resistant material varnish Example: 2 A photosensitive heat-resistant material varnish was prepared as follows using each component in the proportions shown in Table 2.

Polyimide resin A1. Og was dissolved in 35 g of N-methyl-2-pyrrolidone. To this solution, a solution of 2 g of naphthoquinone diazide compound (I-5) dissolved in 10 g of cellosolve acetate as a photosensitizer was added, and after stirring thoroughly,
0, 5! Pressure filtration with a membrane filter of
A photosensitive heat-resistant material varnish was prepared.

Examples 3 to 7 In the same manner as in Example 2, photosensitive heat-resistant material varnishes were prepared using each component in the proportions shown in Table 2.

Comparative Example 2 Polyimide resin AI (Ig) was dissolved in 35 g of N-methyl-2-pyrrolidone. To this solution, 2 g of a naphthoquinonediazide compound (Conventional Example 1, however, the average introduction rate of naphthoquinonediazide was 75%) was added to cellosolve acetate as a photosensitizer. After adding the solution dissolved in 10g and stirring thoroughly,
A photosensitive heat-resistant material varnish was prepared by pressure filtration using a 0.51 membrane filter.

(e) Pattern processing test Each varnish of Examples 2 to 7 was spin-coded onto a 4-inch silicon wafer to a film thickness of 41 mm,
Let dry for a minute. Next, an exposure device (manufactured by Canon, PLA
Ultraviolet rays (4Q5n) pass through a prescribed mask from
i, Il, 0IIIW/cm2) for 40 seconds. The wafer was developed with 3% tetramethylammonium hydroxide for 60 seconds. As a result, in all cases, good patterns were obtained with almost no corrosion in the unexposed areas. Furthermore, at 90℃ for 30 minutes and at 1.50℃ for 30 minutes.
Heat treatment was performed at 250° C. for 30 minutes and at 320° C. for 30 minutes. As a result, there was no pattern disturbance in any case, and line widths of 3 to 5 lines could be sufficiently identified.

These results are summarized in Table 2.

Table 2 (b'J M amount reduction test After coating the photosensitive heat-resistant materials of Examples 2 and 3 on a wafer, the temperature was sequentially heated to 90°C for 30 minutes, 150°C for 30 minutes, and 250°C.
The weight loss of the polyimide film heat-treated at ℃ for 30 minutes and 320℃ for 30 minutes was measured using a thermobalance (in N2 gas, temperature increase rate lO
61° C./min). As a result, the 5wt% weight loss temperature was 463°C in Example 2 (using polyimide resin A) and 459°C in Example 3 (using polyimide resin B).

(c) Adhesion Test Using the photosensitive heat-resistant materials of Example 2.3 and Comparative Example 1, the following evaluations were performed.

■Adhesion with PSG (phosphosilicate glass) film A solution of photosensitive heat-resistant material is coated on the silicon wafer on which the PSG film is formed, using a spin code method, and two square P
, place a silicon chip with SG film on it, dry it at 90℃ for 30 minutes, dry it at 150℃ for 30 minutes, and dry it at 250℃ for 1 hour.
Heat treatment at 50℃ for 30 minutes (2, a polymer film adjusted to about 5 pores was formed.
After allowing the sample to stand for a period of time, the shear fracture strength of the two-angle chip was measured.

■Adhesion with epoxy resin for semiconductor encapsulation A solution of photosensitive heat-resistant material is coated on a silicon wafer on which a PSG film is formed using a spin code method, and dried at 90°C for 30 minutes.
50°C for 30 minutes, 250°C for 1 hour and 350°C for 3 hours.
The polymer film was heat-treated for 0 minutes to form a polymer film having a particle diameter of about 51. Next, this polyimide film-coated silicate blade -/
) was diced into a size of 101 x 30 cm and molded at 175°C for 213 minutes at 80 kg/(1) using a low-pressure transfer molding machine using an epoxy mold for semiconductor encapsulation, resin LKE300TS, product name manufactured by Toshiba Chemical Co., Ltd. Molding conditions′
ζ The above-mentioned silicone: Form a sealing resin of 3 l1In squares (Also, as in Another test after 200 hours of broadcasting.

Next, the shear fracture strength of the sealing resin was measured.

These results are summarized in the table below and are indicated by A.

Table 'B [Effects of the invention 1 Detailed description above j1. As mentioned above, the lift quinone diazide derivative constituting the photosensitizer of the present invention is a new compound that has high sensitivity in the long wavelength region, and is applied to, for example, Trecyst [7, 8. It is possible to form a pattern. Furthermore, the photosensitive heat-resistant abrasive of the present invention has excellent exposure sensitivity, so it is possible to process bright patterns, and it also has excellent adhesion to semiconductor substrates and sealing resins. (1, Therefore, this photosensitive heat-resistant material 1
1. In the resin-sealed conductor device used as a protective film (A
1) Since the humidity level can be greatly improved and cracking of the sealing resin can be prevented, reliability can be greatly improved, and its industrial value is extremely large.

[Brief explanation of drawings]

FIG. 1 is an IR spectrum diagram of the photosensitizer in Example 1 of the present invention.

Claims (3)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, A represents a divalent organic group, and D is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ). (2) (a) General formula (II) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, Z represents a tetravalent organic group having at least 2 carbon atoms, and Y represents at least A photosensitive heat-resistant material comprising: a polyimide having a repeating unit represented by (representing a divalent organic group having one hydroxyl group); and (b) a photosensitizer according to claim (1). (3) A resin-sealed semiconductor device characterized in that the surface of a semiconductor substrate on which an element is formed is coated with the photosensitive heat-resistant material according to claim (2) as a protective film, and further sealed with a molding material resin. .