JP3011457B2 - Photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a photosensitive resin composition for forming a polyimide film pattern used for a protective film in a semiconductor device.

(Prior Art) In a semiconductor device, a process of providing a protective film on a device surface is performed for the purpose of protecting the device from the influence of an external environment and improving its reliability. Conventionally, as a material of the protective film, generally, silicon dioxide, silicon nitride,
An inorganic material such as alumina is used. For example, a general-purpose resin-sealed semiconductor device has a structure in which a protective film using the above-mentioned inorganic material is formed on the semiconductor substrate, and further sealed with an epoxy resin composition or the like. But,
In this case, the epoxy sealing resin has a property of transmitting moisture, and cracks are generated in the protective film due to a difference in thermal expansion coefficient between the sealing resin and the semiconductor substrate as the size of the semiconductor element pellet increases. Easy to do. For this reason, in the semiconductor device, moisture enters from the outside, and corrosion of the wiring pattern formed of aluminum or the like occurs.

As a countermeasure against such a problem, a prescription has been made to further form a protective film using a polyimide resin on the protective film formed of the inorganic material. Polyimide resins are excellent in electrical properties such as insulating properties, radiation resistance, and heat resistance, and thus have been widely used in recent years as the protective film, and are particularly useful as heat resistant materials. Also, polyimide resins are widely used as interlayer insulating films in a multilayer wiring structure of a semiconductor device due to the above characteristics.

The polyimide resin as described above can be easily formed into a film from a polyamide wire as a precursor.
That is, first, the varnish of the polyamic acid is applied to a predetermined surface and heated to form a film.
Further, a heat treatment is performed to cure the precursor polyamic acid by a cyclization reaction to form a polyimide film. This method is widely used because a stabilization process at a relatively low temperature can be employed.

On the other hand, in semiconductor devices, pad processing for conducting through holes in a multilayer wiring structure and external leads is required. Therefore, the polyimide film formed as a protective film or an interlayer insulating film in the semiconductor device requires processing such as patterning or forming a hole. Usually, the patterning of the polyimide film is performed using PEP (photo engraving p
rocess). That is, after a polyimide film is formed on a semiconductor surface by the above method, a photoresist film is provided on the surface, and the photoresist film is exposed and exposed.
Develop to form a resist pattern. Then, using the resist pattern as an etching-resistant mask, the underlying polyimide film is selectively etched to form a polyimide protective film or an interlayer insulating film having a desired pattern.

However, in the method of forming a polyimide film pattern as described above, the formation of a polyimide film and
It is necessary to perform PEP and two independent processes,
The operation is complicated by multi-step processes.

In order to solve such a drawback in the process, a resin composition containing a polyimide precursor which enables patterning of a polyimide film without using PEP has been disclosed.

For example, JP-A-49-115541 discloses a polyamic acid ester having a repeating unit represented by the following general formula (III).

This polyamic acid ester is replaced with a tetracarboxylic dianhydride which is usually used in the process of synthesizing a polyamic acid which is a polyimide precursor, and a dichlorinated product of a dicarboxylic diester in which a group having photopolymerizability is introduced by an ester bond. And a diamino compound, and has a negative photosensitive performance in which exposed portions are insoluble in a developing solution. However, in this polyamic acid ester, the process of synthesizing the compound containing the photopolymerizable group and the process of synthesizing the polyamic acid ester are complicated, and furthermore, chlorine ions are contained as impurities in the final resin product. There is a disadvantage that.

In addition, as a negative photosensitive resin composition,
JP-A-59-52822 describes a heat-resistant photosensitive material containing a compound containing a carbon-carbon double bond and an amino group that can be duplicated or polymerized by electromagnetic waves. However, when this photosensitive material is used as the protective film in a resin-encapsulated semiconductor device, it has a problem that the reliability of the semiconductor device is impaired due to poor adhesion to a semiconductor substrate or a sealing resin. .

On the other hand, a polymer having an isoimide structure is disclosed in JP-A-62-145240 as a compound having a positive photosensitive property in which an exposed portion becomes soluble in a developing solution. However, this polymer has the disadvantages of low heat resistance and low exposure sensitivity.

JP-A-64-60630 discloses a composition obtained by adding an o-quinonediazide compound as a photosensitizer to a solvent-soluble imide synthesized from a diamine compound having a hydroxyl group on an aromatic ring and an acid anhydride. Have been. However, since the precursor polyamic acid is soluble in an alkali developer, this composition needs to be an imidized polymer in order to impart positive photosensitive performance. Since a large amount of time is required for the polymer synthesis process, there is a problem that productivity is poor.

(Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to solve the above-mentioned conventional disadvantages and to provide a fine and An object of the present invention is to provide a photosensitive resin composition capable of forming a polyimide film pattern having high resolution and having excellent exposure sensitivity to light irradiation.

A further object of the present invention is to provide a photosensitive resin composition capable of forming the polyimide film pattern having excellent adhesion and moisture resistance with a substrate and a sealing resin as a protective film in a semiconductor device. is there.

[Configuration of the invention]

(Means for Solving the Problems) The first photosensitive composition of the present invention comprises: (a) a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (I '): A polyamic acid having a copolymer structure containing: (b) at least one acid generator selected from the group consisting of onium salts and organic halogen compounds; and (c) orthoquinone diazide sulfonic acid ester and orthoquinone diazide sulfonic acid. A photosensitive resin composition comprising at least one photosensitive agent selected from the group consisting of amide esters.

Here, R ^{1 to} R ³ indicate the following, respectively.

R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group The second photosensitive composition of the present invention (A ') a repeating unit represented by the following general formula (I); a repeating unit represented by the following general formula (I');
Selected from the group consisting of a polyamide-amic acid having a copolymer structure containing a repeating unit represented by I) and a repeating unit represented by the following general formula (II '); and (b) an onium salt and an organic halogen compound. And (c) at least one photosensitizer selected from the group consisting of orthoquinonediazidesulfonic acid ester and orthoquinonediazidosulfonic acid amide ester. It is a resin composition.

OCNH-R ¹ -NHCO-R ⁴ (II) OCNH-R ² -NHCO-R ⁴ (II ′) wherein R ^{1 to} R ⁴ represent the following, respectively.

R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group R ⁴ : a divalent organic group The details of the photosensitive resin composition of the present invention will be described.

The photosensitive resin composition of the present invention contains a resin component, an acid generator, and a photosensitive agent component. Of these, components other than the resin component are common in the first and second photosensitive resin compositions, but the resin components are different. That is, the resin component in the first photosensitive resin composition is a polyamic acid (a), and the resin component in the second photosensitive resin composition is a polyamide amic acid (a ′).
The polyamic acid (a) is a repeating unit represented by the general formula (I), and the polyamide-amic acid (a ') is a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) Includes each unit. The photosensitive resin composition of the present invention, the organic group R ¹ in these repeating units in the resin component (a) and (a ') is characterized in that it has at least one phenolic hydroxyl group. Therefore,
First, the resin component in the photosensitive resin composition of the present invention will be described.

The resin component in the first photosensitive resin composition of the present invention is a polyamide having a copolymer structure containing a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (I ') Acid (a). This polyamic acid (a) is a precursor of polyimide and has the following general formula (I)
V) a diamine having a phenolic hydroxyl group represented by the following general formula (IV ′), a diamine containing no phenolic hydroxyl group represented by the following general formula (IV ′), and a tetracarboxylic dianhydride represented by the following general formula (V) It is synthesized by a polycondensation reaction in a solvent.

^{HN-R 1 -NH (IV)} HN-R 2 -NH (IV ') Here, R ^{1 to} R ³ indicate the following, respectively.

R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group As the diamine (IV) having the phenolic hydroxyl group Is not particularly limited, for example, 3,3 '
-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-
Diamino-4,4'-dihydroxybiphenyl, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-hydroxy-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, 3,3'-dihydroxy-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) hexafluoropropane, -Hydroxy-4,
4'-diaminodiphenyl sulfone, 3-hydroxy-
At least one diamine selected from the group consisting of 4,4'-diaminodiphenyl ether and 3-hydroxy-4,4'-diaminodiphenylmethane can be used.

Diamine (IV ') containing no phenolic hydroxyl group
Is not particularly limited, for example, m
-Phenylenediamine, p-phenylenediamine, 2,4
-Tolylenediamine, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,
4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 1 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4- Aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-
Dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, (Or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenyl Urea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,
2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy)
Diphenylsphone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy Aromatic diamines such as diphenylsulfone, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, and the aromatic nucleus hydrogen atom of these aromatic diamines is chlorine atom, fluorine atom, bromine atom A compound substituted by at least one substituent selected from the group consisting of a methyl group, a methoxy group, a cyano group and a phenyl group, dimethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, Octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1, 2- bis (3'-amino propoxy) _{ethane, H 2 N- (CH 2)} 3 -O- (CH 2) 2
—O— (CH ₂ ) ₃ —NH ₂ , 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 4,4′-diamino Dicyclohexylmethane, 4,
4'-diaminodicyclohexylisopropane, 1,4-xylylenediamine, 2,6-diaminopyridine, 2,6-diamino-s-triazine, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis At least one diamine selected from the group consisting of (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane can be used.

The amount of the diamine (IV) having a phenolic hydroxyl group to be used is desirably 50 mol% or more of the total amount of the diamine used for synthesizing the photosensitive resin composition of the present invention. The reason for this is that the amount of the diamine (IV) used is
If it is less than 50 mol%, the final photosensitive resin composition
The tetracarboxylic dianhydride (V) is not particularly limited because sufficient photosensitivity is not provided. 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, bis (3,4-dicarboxyphenyl)
Ether dianhydride, 2,2-bis (3 ', 4'-dicarboxyphenyl) propane dianhydride, 2,2-bis (3', 4 '
-Dicarboxyphenyl) hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-di (Carboxyphenyl) tetramethyldisiloxane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride At least one compound selected from the group consisting of:

In the polycondensation reaction for synthesizing the polyamic acid (a), the total amount of the diamine (the sum of the diamine (IV) having a phenolic hydroxyl group and the diamine (IV ') not containing a phenolic hydroxyl group) and tetracarboxylic dianhydride (V)
Is preferably in the range of 0.9 to 1.1: 1 in terms of molar ratio.

In the polycondensation reaction for synthesizing the polyamic acid (a) using each of the above raw materials, the repeating unit (I) is formed by the reaction of the diamine (IV) having a phenolic hydroxyl group and the tetracarboxylic dianhydride (V). The repeating unit (I ') is formed by the reaction of a diamine (IV') containing no phenolic hydroxyl group and a tetracarboxylic dianhydride (V). At this time, when the diamine having a phenolic hydroxyl group (IV) and the diamine having no phenolic hydroxyl group (IV ′) and the tetracarboxylic dianhydride (V) are used in various types, the above-mentioned repetition is formed. Each of the units (I) and (I ′) can also be formed in various types.

Further, in the polyamic acid (a) synthesized by the polycondensation reaction, regarding the copolymer structure formed by the repeating units (I) and (I ′), a random copolymer, a block copolymer, or Any structure of a copolymer in which both are used can be used.

Examples of the organic solvent used in the polycondensation reaction for synthesizing the polyamic acid (a) include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-
2-pyrrolidone, N-methyl-ε-caprolactam, γ
-Butyrolactone, sulfolane, N, N, N ', N'-tetramethylurea, hexamethylphosphoramide, tetrahydrofuran, cyclohexanone, dioxane and the like. The conditions for the polycondensation reaction are generally adjusted within a range of a reaction temperature of −20 to 100 ° C. and a reaction time of 10 minutes to 20 hours.

As described above, the polyamic acid (a) as the resin component in the first photosensitive resin composition of the present invention can be synthesized by a simple process such as a polycondensation reaction by elimination of water molecules. As a result, it is preferable in that the content of residual impurities in the obtained photosensitive resin composition is reduced.

The resin component in the second photosensitive resin composition of the present invention includes a repeating unit represented by the general formula (I), a repeating unit represented by the general formula (I '), and a resin represented by the general formula (II)
A polyamide / amic acid (a ′) having a copolymer structure containing the repeating unit represented by the general formula (II ′) and the repeating unit represented by the general formula (II ′). This polyamic acid (a ′) is a precursor of a polyimide / polybenzoxazole copolymer, and is represented by the following general formula (IV ′) with a diamine having a phenolic hydroxyl group represented by the following general formula (IV) A polycondensation reaction of a diamine containing no phenolic hydroxyl group, a tetracarboxylic dianhydride represented by the following general formula (V), and a dicarboxylic dichloride represented by the following general formula (VI) in an organic solvent. Synthesized.

^{HN-R 1 -NH (IV)} HN-R 2 -NH (IV ') ClOC-R ⁴ -COCl (VI) where, R ¹ to R ⁴ denotes those respective following.

R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group R ⁴ : a divalent organic group In the synthesis of the amic acid (a '),
The diamine having a phenolic hydroxyl group (IV), the diamine having no phenolic hydroxyl group (IV '), and the tetracarboxylic dianhydride (V) are used for the synthesis of the polyamic acid (a), respectively. Similar compounds can be used. At this time, the diamine (IV) and
As with the case of the synthesis of the polyamic acid (a), the use amount of the diamine (IV) having a phenolic hydroxyl group is also important for the synthesis of the photosensitive resin composition of the present invention. Desirably, it is at least 50 mol% of the total amount of diamine used.

Further, as the dicarboxylic acid dichloride (VI),
Although not particularly limited, terephthalic acid dichloride, isophthalic acid dichloride, diphenyl ether-4,
4'-dicarboxylic acid dichloride, diphenyl sulfone-
4,4'-dicarboxylic acid dichloride, biphenyl-4,4'-
At least one compound selected from the group consisting of dicarboxylic acid dichloride, naphthalene-2,6-dicarboxylic acid dichloride, pyridine-2,6-dicarboxylic acid dichloride, and thiophene-2,5-dicarboxylic acid dichloride can be used.

In the polycondensation reaction for synthesizing the polyamide-amic acid (a ′), the total amount of diamines (the total amount of the diamine (IV) having the phenolic hydroxyl group and the diamine (IV ′) not containing the phenolic hydroxyl group) is It is preferable that the amount is equimolar to the total amount of tetracarboxylic dianhydride (V) and dicarboxylic dichloride (VI).

In the polycondensation reaction for synthesizing the polyamide-amic acid (a ') using each of the raw materials described above, the repeating unit (I) is formed by the reaction of the diamine (IV) having a phenolic hydroxyl group and the tetracarboxylic dianhydride (V). The repeating unit (I ') has a phenolic hydroxyl group by the reaction of a diamine (IV') containing no phenolic hydroxyl group and a tetracarboxylic dianhydride (V).
V) and the dicarboxylic acid dichloride (VI) to form the repeating unit (II) into a diamine (IV ') containing no phenolic hydroxyl group and a dicarboxylic acid dichloride (V
The repeating unit (II ′) is formed by the reaction of I). In this case, the diamine (IV) having a phenolic hydroxyl group, the diamine (IV ') not containing a phenolic hydroxyl group, the tetracarboxylic dianhydride (V), and the dicarboxylic dichloride (VI) are used in various types. The repeating units (I), (I '), (I
Each of I) and (II ') can also be formed in various types.

In the polyamide-amic acid (a ') synthesized by the polycondensation reaction, the repeating units (I) and (I')
Regarding the copolymer structure formed by (II) and (II ′), a random copolymer, a block copolymer,
Alternatively, any structure of a copolymer in which both are used can be used. However, in the polyamide-amic acid (a ′), the total content of the amide acid repeating units (I) and (I ′) is 0.1 to 99.9 mol%, preferably 1.0 to 90 mol%, more preferably 20-85 mol%. This is because if the content is less than 0.1 mol%, the photosensitive properties of the finally produced photosensitive resin composition tend to be inferior, and if it exceeds 99.9 mol%, the high molecular weight ratio of the polymer becomes low. This is because it becomes difficult to form a protective film having good performance.

As the organic solvent used in the polycondensation reaction for synthesizing the polyamide-amic acid (a '), the same organic solvents as those used for synthesizing the polyamic acid (a) can be used. The same reaction conditions as in the synthesis of the polyamic acid (a) are used for the reaction conditions in the synthesis of the polyamide-amic acid (a ').

In the polycondensation reaction for synthesizing the polyamide-amic acid (a '), a reaction between a diamine (IV) having a phenolic hydroxyl group and a dicarboxylic acid dichloride (VI), and a diamine (IV) containing no phenolic hydroxyl group ') And dicarboxylic acid dichloride (VI) produce hydrochloric acid as a by-product. Therefore, in the polycondensation reaction, in order to capture the hydrochloric acid, an equivalent amount of the hydrochloric acid to 20 or less.
A molar% excess of alkylene oxide is used. As the alkylene oxide, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, isobutylene oxide and the like can be used.

In the second photosensitive resin composition of the present invention synthesized as described above, the polyamide / amic acid (a ′) in the resin component contains the repeating units (II) and (I) in the molecule.
Since a polyamide unit such as I ′) is contained, the molecular weight of the resin component is further increased. For this reason, it is preferable in that the heat resistance of the finally obtained polyimide / polybenzoxazole copolymer film and the adhesion in the semiconductor device are improved.

Next, the acid generator (b) of the photosensitive resin composition of the present invention will be described. The acid generator (b) is usually used as the resin component in the first photosensitive resin composition of the present invention, the polyamic acid (a) or the resin component in the second photosensitive resin composition. It has the property of suppressing the alkali solubility of a certain polyamide amide acid (a ') and generating an acid upon irradiation with light.

As the acid generator (b) used in the present invention, various known compounds and mixtures can be used in common with the first and second photosensitive resin compositions. Specifically, onium salts such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts (all of which are, for example, ▲ SbF ^- ₅ ▼,
▲ PF ^- ₆ ▼, ▲ AsF ^- ₆ ▼, ▲ BF ^- ₄ ▼, CF ₂ ▲ SO ^- ₃ ▼ like what you counterion), organic halogen compounds, p- quinone diazide compounds and the like.

Examples of the diazonium salt include salts of benzenediazonium, p-chlorobenzenediazonium, p-bromobenzenediazonium, o-, m-, or p-methylbenzenediazonium, p-methoxybenzenediazonium, p-dimethylaminobenzenediazonium, That is, arsenic hexafluoride, boron tetrafluoride, phosphate hexafluoride, benzenediazonium paratoluenesulfonate, 4- (di-n-propylamino) -benzenediazonium tetrafluoroborate, 4-p-
Tolyl mercapto-2,5-diethoxybenzenediazonium hexafluorophosphate, diphenylamine-4
-Diazonium sulphate and the like can be used.

Examples of the onium salt include diphenyliodonium trifluoromethanesulfonate, bis (t-butylphenyl) iodonium trifluoromethanesulfonate, p-bis (pt-butylphenyl) diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium Fluoromethanesulfonate, tri (t-butylphenyl) sulfonium trifluoromethanesulfonate, JP-A Nos. 50-36209 and 54-74728
No. 55-24113, No. 55-77742, No. 56-1734
No. 5, No. 60-3626, No. 60-138538, No. 63-250
Illustrative compounds described in JP-A-642 can be used.

Examples of the organic halogen compound include 4-methyl-6-trichloromethyl-2-pyrone and 4- (3,4,5
-Trimethoxy-styryl) -6-trichloromethyl-
2-pyrone, 4- (4-methoxy-styryl) -6
(3,3,3-trichloro-propenyl) -2-pyrone, 2
-Trichloromethyl-benzimidazole, 2-tribromomethyl-quinolone, 2,4-dimethyl-1-tribromoacetyl-benzene, 4-dibromoacetyl-benzoic acid, 1,4-bis-dibromomethyl-s-triazine, 2
-(6-methoxy-naphthyl-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (naphthyl-1-yl) -4,6-bis-trichloromethyl-s-triazine, -(Naphthyl-2-yl) -4,6-bis-
Trichloromethyl-s-triazine, 2- (4-ethoxyethyl-naphthyl-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (benzopyran-3
-Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-anthrac-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2-
(Phenanth-9-yl) -4,6-bis-trichloromethyl-s-triazine, U.S. Pat.
Nos. 6,489,3779778 and West German Patent Publication No.2243621 can be used.

As the p-quinonediazide compound, for example, 2,
6-Dimethyl-p-quinonediazide, 2,6-di-t-butyl-p-quinonediazide and the like can be used.

Next, the photosensitive agent component (c) of the photosensitive resin composition of the present invention
Will be described. As the photosensitive agent component (c) used in the present invention, for example, various known o-quinonediazide compounds can be used in common with the first and second photosensitive resin compositions.

Examples of the o-quinonediazide compound include, for example, U.S. Pat.Nos. 2,766,118, 2,677092, 2,772972, 2,285,912, 2,907,665, 3,046,110, and 304.
Compounds described in JP-A Nos. 6111, 3046115 and 3647443 can be used.

Further, as the o-quinonediazide compound, for example,
The following compounds (NQ-1) and (NQ-2) and compounds represented by the following general formula (VII) can be used.

Here, A and D indicate the following, respectively.

A: divalent organic group Among the o-quinonediazide compounds represented by the general formula (VII), the following general formula (VII-1) or (VII-2)
1,2-naphthoquinone-2-diazide-4- represented by
An amide ester compound of (or -5) sulfonic acid is particularly desirable.

Where R is Is shown.

(Hydrogen atom of each aromatic nucleus in the above R is an alkyl group, a halogen atom may be those substituted with hydroxy group, X in the above R is a direct _{bond, -O -, - CH 2 -} , - SO _2- ,
-CO-, Or Represents The photosensitive resin composition of the present invention comprises, in addition to the components (a) or (a ') to (c), a dissolution inhibitor containing, if necessary, an organic compound having a substituent which is decomposed by an acid. May be contained. The dissolution inhibitor may be a polyamic acid (a) that is a resin component in the first photosensitive resin composition of the present invention, or a polyamide-amic acid (a resin component) in the second photosensitive resin composition. a ′) is to suppress the alkali solubility. Here, acid
The acid generator (b) corresponds to an acid generated by light irradiation.

Examples of the organic compound having a substituent that is decomposed by an acid include, for example, poly-t- described in U.S. Pat.
Butyl vinyl benzol, poly-t-butoxycarbonyloxystyrene and the corresponding α-methylstyrene polymer; poly-t-butoxystyrene and poly-t-butoxy-α-methylstyrene described in U.S. Pat. A polyacrylate having a butyl ester group or a benzyl ester group, a polymer having the acid labile group in the main chain or as a side group corresponding to the main chain; a carbonate side group such as a t-butoxycarbonyloxy group or a trimethylsilyl ether side; Aromatic polymers having a group; compounds (D-1) to (D-42) shown in Table A below can be used.

In addition to the above, the photosensitive resin composition of the present invention may optionally contain various additives such as a surfactant and a silane coupling agent as a coating film modifier, and a dye as an antireflection agent. obtain.

The photosensitive resin composition of the present invention, the resin component described above,
Prepared in the form of a varnish by dissolving an acid generator component, a photosensitizer component, a dissolution inhibitor containing an organic compound having a substituent that can be decomposed by an acid if necessary, and other additives in an organic solvent. Is done.

In the preparation of the photosensitive resin composition of the present invention, the amount of the resin component (polyamic acid (a) or polyamide-amic acid (a ')) is adjusted as follows. That is, in the varnish, the concentration of the polymer (resin component) is desirably adjusted to 5 to 40% by weight.

In the preparation of the photosensitive resin composition of the present invention, the amount of the acid generator (b) is adjusted as follows. That is, in any case of the first photosensitive resin composition or the second photosensitive resin composition, 0.01 to 40% by weight, more preferably 0.01 to 40% by weight, based on the total solid content of the photosensitive resin composition. Is adjusted in the range of 0.1 to 30% by weight. The reason for this is that if the amount of the acid generator (b) is less than 0.01% by weight, the effect of suppressing the alkali solubility of the photosensitive resin composition of the present invention in the resin component is insufficient. If the content exceeds 30% by weight, the applicability of the obtained photosensitive resin composition deteriorates, and it becomes difficult to form a coating film having a uniform thickness.

In the preparation of the photosensitive resin composition of the present invention, the amount of the photosensitive agent (c) is adjusted as follows. That is, in any case of the first photosensitive resin composition or the second photosensitive resin composition, 1 to 40% by weight, more preferably, based on the total weight of the solid content of the photosensitive resin composition. Is adjusted in the range of 3 to 25% by weight. The reason for this is that if the amount of the photosensitive agent (c) is outside the above range, sufficient photosensitive performance is not provided to the obtained photosensitive resin composition.

In addition, in the preparation of the photosensitive resin composition of the present invention, when the prepared photosensitive resin composition contains a dissolution inhibitor containing an organic compound having a substituent that is decomposed by the acid, the dissolution inhibition is suppressed. The amount of the agent is adjusted as follows. That is, 100 parts by weight of the polyamic acid as the resin component in the case of the first photosensitive resin composition, or 100 parts by weight of the polyamide-amic acid as the resin component in the case of the second photosensitive resin composition. On the other hand, it is adjusted in the range of 0.5 to 200 parts by weight, preferably 1 to 100 parts by weight. The reason is that if the compounding ratio is less than 0.5 part by weight, sufficient developing performance is not imparted to the obtained photosensitive resin composition,
On the other hand, if the compounding ratio exceeds 200 parts by weight, the applicability of the obtained photosensitive resin composition deteriorates, and it becomes difficult to form a coating film having a uniform thickness.

In the preparation of the varnish of the photosensitive resin composition of the present invention, the organic solvent used includes an organic solvent used for synthesizing the polyamic acid (a) or the polyamide-amic acid (a ′), and a ketone-based solvent. (Cyclohexanone, acetone, methyl ethyl ketone, etc.), cellosolve solvents (methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, etc.), and ester solvents (ethyl acetate, butyl acetate, isoamyl acetate, etc.) alone or in a mixture. Can be used in form.

(Operation) Hereinafter, the operation of the photosensitive resin composition of the present invention will be described along the step of forming a protective film or an interlayer insulating film in a semiconductor device or the like using the composition. This description of the operation is common to the first and second photosensitive resin compositions of the present invention unless otherwise specified.

The following description of the operation is provided for the purpose of facilitating the understanding of the present invention, and includes an uncertain hypothesis. Accordingly, the invention is not limited by the specific theory or mechanism contained in the following description.

First, as a first step, the photosensitive resin composition of the present invention is prepared as a varnish according to the above method.

At this point, in the first photosensitive resin composition of the present invention, the o-quinonediazide compound (o-naphthoquinonediazidesulfonic acid ester) of the photosensitizer (c) is used.
Has reacted with the phenolic hydroxyl group in R ¹ contained in the repeating unit (I) of the polyamic acid (a) of the resin component. By this reaction, the function of the carboxyl group -COOH contained in the repeating unit (I) of the polyamic acid (a) is inhibited. Therefore, in the photosensitive resin composition, the function of the composition as an acid as a whole is reduced, and the alkali solubility is suppressed. Further, the acid generator (b) also has an action of suppressing alkali solubility in the polyamic acid (a) as a resin component.

Further, in the second photosensitive resin composition of the present invention, the o-quinonediazide compound (o-naphthoquinonediazidesulfonic acid ester) of the photosensitizer (c) is converted to the polyamide-amic acid (a ′) of the resin component. It is reacted to the phenolic hydroxyl group in R ¹ contained in the repeating units (I) and (II). By this reaction, the function of the carboxyl group -COOH contained in the repeating units (I) and (II) of the polyamide-amic acid (a ') is inhibited as described above. Therefore, in the photosensitive resin composition, the function of the composition as an acid as a whole is reduced, and the alkali solubility is suppressed. Further, the acid generator (b) also has an action of suppressing alkali solubility in the polyamide-amic acid (a ') as a resin component.

Next, as a second step, the photosensitive resin composition varnish, after removing fine contaminants in the composition by filtration or the like, spin coating method, dipping method, screen printing method, etc., on the substrate, Apply. Further, by drying this, the photosensitive resin composition layer of the present invention is formed. As the substrate used here, for example, a silicon wafer,
Examples include a group III-V compound semiconductor wafer such as GaAs and AlGaAs, a wafer having various insulating films, electrodes, and wirings formed on its surface, a substrate used for electronic components such as a printed wiring board, and a semiconductor device.

Next, as a third step, after precuring the photosensitive resin composition layer, the surface of the layer is selectively irradiated with energy rays via a desired mask pattern. Examples of the energy ray include visible light, ultraviolet light, excimer laser (for example, XeF (wavelength 351 nm), KrF (wavelength 248 nm), Ar
Deep UV such as F (wavelength 193 nm), X-ray, electron beam, and the like are used. Here, for the electron and the beam, pattern exposure can be performed by scanning the beam without using the mask pattern.

When the energy ray is irradiated, the acid generator (b) generates an acid by light irradiation in the exposed portion of the photosensitive resin composition layer of the present invention. Further, at the branched terminal of the exposed portion, the o-naphthoquinonediazidosulfonic acid ester portion (VIII) of the photosensitizer (c) is converted into carboxylic acid (ketene (IX) by photochemical reaction and water in the system. X). The following shows the progress of the above reaction.

Subsequently, as a fourth step, the exposed photosensitive resin composition is subjected to a development treatment by an immersion method using an aqueous alkaline solution, a spray method, or the like. Examples of the alkaline developer include aqueous quaternary ammonium salts such as aqueous tetramethylammonium hydroxide and aqueous trimethylhydroxyethylammonium, sodium carbonate, and the like.
An aqueous solution of an inorganic alkali such as potassium hydroxide or sodium hydroxide can be used. These developers are usually used at a concentration of 15% by weight or less.

Here, in the non-exposed part of the photosensitive resin composition, the o-naphthoquinonediazide of the acid generator (b) and the photosensitive agent (c) is inhibited from dissolving in the alkaline aqueous solution by the light irradiation as described above. Works as an agent. For this reason, the unexposed portions of the photosensitive resin composition are hardly dissolved in the alkali developing solution.

On the other hand, in the exposed portion of the photosensitive resin composition, the acid generator (b) generates an acid at the branched terminal, and the carboxylic acid (X) is converted by the photoreaction of o-naphthoquinonediazide described above. Has occurred. These acids react with alkali metal ions or ammonium ions in the alkali developer to form salts and dissolve the exposed portions. Therefore, only the non-exposed portion of the photosensitive resin composition layer remains by this developing treatment. That is, the photosensitive resin composition of the present invention has a function as a positive photosensitive material in which the exposed portion becomes soluble in a developer.

Thus, by the photosensitive resin composition of the present invention,
A desired relief pattern is formed.

As described above, the photosensitive resin composition of the present invention may contain a dissolution inhibitor containing an organic compound having a substituent that is decomposed by the acid. This dissolution inhibitor further suppresses the solubility of the photosensitive resin composition in an alkali-exposed solution in the unexposed portion of the photosensitive resin composition in the above-described development processing. On the other hand, in the exposed portion of the photosensitive resin composition, the dissolution inhibitor loses its dissolution inhibiting effect on the alkali developer because the acid generator (b) is decomposed by the action of the acid generated by light irradiation. . For this reason, when the photosensitive resin composition of the present invention contains the dissolution inhibitor,
In addition to the action of the acid generator (b) and the photosensitive agent (c), the non-exposed portion promotes insolubility in a developer. Further, the solubility in the developing solution is promoted in the exposed portion. That is, the difference in solubility of the photosensitive resin composition between the exposed portion and the non-exposed portion with respect to the developing solution,
Be larger. Accordingly, the photosensitive resin composition of the present invention preferably contains a dissolution inhibitor as described above, if necessary.

After the above-mentioned development processing step, for the purpose of removing the developer residue, a rinsing treatment using water, alcohol, acetone or the like may be performed, followed by a treatment such as baking.

Next, as a fifth step, the photosensitive resin composition layer having a predetermined pattern developed as described above, 100 to 4
The heat treatment is performed at 00 ° C., preferably 250 ° C. or less. By this treatment, the amide acid is closed in the repeating units (I) and (I ') in the resin component of the photosensitive resin composition of the present invention. Thus, a polyimide film (in the case of the first photosensitive resin composition) or a polyimide / polybenzoxazole copolymer film (the second photosensitive resin) containing a repeating unit represented by the following general formula (XI) having a predetermined pattern. (In the case of a conductive resin composition).

By performing processing such as sealing using a sealing resin such as an epoxy resin according to a conventional method, the semiconductor substrate having the polyimide film formed on the surface according to the above method,
A resin-sealed semiconductor device is manufactured.

In such a semiconductor device, the patterned polyimide film has excellent electric insulation, radiation resistance, heat resistance, and adhesion, and thus suitably functions as a protective film or an interlayer insulating film.

As described above, the photosensitive resin composition of the present invention has two functions as a positive photoresist and as a polyimide film for a protective film or an interlayer insulating film of a semiconductor device or the like. Therefore, when the photosensitive resin composition of the present invention is used, in forming a protective film or an interlayer insulating film of a semiconductor device or the like, two steps of a photoresist process for forming a pattern and a film forming process are performed on a semiconductor substrate. The application of the substance and the respective treatments can be performed continuously. In this way, the simplification of the above steps is achieved.

(Examples) Hereinafter, examples of the photosensitive resin composition according to the present invention will be described in detail.

In addition, various compounds (acid generators b-1 and b-2, photosensitive agent c-1) used in the following Examples and Comparative Examples below.
And the contents of c-2 and the dissolution inhibitors d-1 and d-2) are shown in Table B below.

Synthesis Example 1 (Preparation of Polyamic Acid Resin Varnish A) In a reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel, 16.110 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was placed. ), 10.906 g (0.05 mol) of pyromellitic dianhydride and 100 g of N-methyl-2-pyrrolidone were cooled to 0 ° C. with sufficient stirring. Subsequently, the suspension was kept at 0 ° C.
3,5.795 g (0.095 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and bis (γ-aminopropyl) tetramethyldisiloxane 1.23
A solution in which 4 g was dissolved in 150 g of N-methyl-2-pyrrolidone was gradually dropped using a dropping funnel. After completion of the dropwise addition, the reaction solution was stirred for 6 hours while maintaining the reaction solution at 0 to 10 ° C. to obtain a polyamic acid resin as a resin component of the first photosensitive resin composition of the present invention in the form of a resin varnish. This is designated as polyamic acid resin varnish A.

Synthesis Example 2 (Preparation of polyamic acid resin varnish B) 32.22 g (0.10 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3'-dihydroxy-4,
17.297 g (0.08 mol) of 4'-diaminobiphenyl and 4,4
3.203 g (0.016 mol) of 4'-diaminodiphenyl ether
, Bis (γ-aminopropyl) tetramethyldisiloxane, 0.994 (0.004 mol), and N-methyl-2-pyrrolidone (210 g) in the same manner as in Synthesis Example 1 above, and the first photosensitive material of the present invention was used. A polyamic acid resin as a resin component of the conductive resin composition was obtained in the form of a resin varnish. This is designated as polyamide acid resin varnish B.

Example 1 Polyamide acid resin varnish A prepared in Synthesis Example 1 was 50 g.
1.0 g of a dissolution inhibitor d-1 and 2.0 g of an acid generator b-1
2.0 g of photosensitizer c-1 was added to 10 g of N-methyl-2-pyrrolidone.
Was added, and the mixture was thoroughly stirred. Next, the reaction solution was filtered under pressure through a membrane filter having a hole diameter of 0.5 μm to prepare a first photosensitive resin composition of the present invention.

Examples 2 to 8 The first photosensitive resin composition of the present invention was prepared using the raw material compositions shown in Table 1 below and in the same manner as in Example 1.

Comparative Example 1 Polyamic acid resin varnish A30 g prepared in Synthesis Example 1
In addition, dissolution inhibitor d-1 0.6 g, acid generator b-1 1.2 g,
N-methyl-2-pyrrolidone (6 g) was added to each, followed by sufficient stirring. Next, the reaction solution was filtered under pressure with a membrane filter having a hole diameter of 0.5 μm to prepare a resin composition of a comparative example with respect to the first photosensitive resin composition of the present invention.

Comparative Example 2 Polyamic acid resin varnish A30 g prepared in Synthesis Example 1 above
In addition, dissolution inhibitor d-1 0.6 g, photosensitive agent c-1 1.2 g, N
-Methyl-2-pyrrolidone (6 g) was added, and the mixture was thoroughly stirred. Next, the reaction solution was filtered under pressure with a membrane filter having a hole diameter of 0.5 μm to prepare a resin composition of a comparative example with respect to the first photosensitive resin composition of the present invention.

The first photosensitive resin composition of the present invention prepared as described above was subjected to the following characteristic tests.

Pattern workability test (resolution evaluation) Photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to
Each varnish of the resin composition No. 2 was spin-coated on a 5-inch diameter silicon wafer to a thickness of 4 μm, and dried at 90 ° C. for 20 minutes. Next, an exposure apparatus (PLA-501
F: manufactured by Canon Inc.), and ultraviolet rays (405 nm, 11.0 mw) were formed on the coating film through a mask having a predetermined pattern.
/ cm ² ) for 40 seconds. Thereafter, the silicon wafer was immersed in an alkali developing solution (3% aqueous solution of tetramethylammonium hydroxide) for 60 seconds to perform a developing process, thereby forming a pattern.

As a result, with respect to the photosensitive resin compositions of Examples 1 to 8, the non-exposed portions were hardly eroded by the developing solution, and good patterns were formed. On the other hand, in the resin compositions of Comparative Examples 1 and 2, all of the exposed and unexposed portions were dissolved by the developer.

Further, for the photosensitive resin compositions of Examples 1 to 8,
90 ° C for 30 minutes, 150 ° C for 30 minutes, 250 ° C for 30 minutes, 320 ° C
For 30 minutes. As a result, in each of the examples, the pattern formed before the heating was not disturbed, and the line width of 3 to 5 μm could be sufficiently identified.

The results of the above characteristic tests in Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 1 below. It was confirmed that each of the polyimide film patterns formed using the first photosensitive resin composition of the present invention had a resolution suitable for a protective film and an interlayer insulating film in a semiconductor device.

Adhesion Test-A (Evaluation of Adhesion with Phosphosilicate Glass Film) Each varnish of the photosensitive resin compositions of Examples 5 to 8 was placed on a silicon wafer having a phosphosilicate glass film (PSG film) formed on the surface. It was applied by spin coating. On the surface
A silicon chip having a 2 mm square PSG film is placed on the coating so that the PSG film is in contact with the coating, and a PSG film /
A laminate having the structure of the photosensitive resin composition layer / PSG film was formed. Next, the laminate was dried at 90 ° C. for 30 minutes, then at 150 ° C. for 30 minutes, at 250 ° C. for 1 hour, and at 350 ° C. for 30 minutes.
A heat treatment was performed for one minute, and a polymer film having a thickness adjusted to about 5 μm was formed between the silicon wafer and the silicon chip. Further, the sample thus obtained was left in a pressure cooker at 120 ° C. and 2 atm. For 100 hours. Pressure cooker process (P
For each of the sample subjected to CT) and the sample not subjected to the pressure cooker, the shear fracture strength of the 2 mm square silicon chip placed as described above was measured.

Adhesion Test-B (Evaluation of Adhesion with Epoxy Resin for Semiconductor Encapsulation) Each varnish of the photosensitive resin compositions of Examples 5 to 8 was placed on a silicon wafer having a phosphosilicate glass film (PSG film) formed on the surface. Was applied by a spin coating method. next,
The sample was dried at 90 ° C. for 30 minutes, and then subjected to heat treatment at 150 ° C. for 30 minutes, 250 ° C. for 1 hour, and 350 ° C. for 30 minutes to form a polymer film having a film thickness adjusted to about 5 μm. Further, a silicon wafer having a polymer film on its surface was diced to a size of 10 mm × 30 mm, and a 3 mm square sealing resin was formed on each sample using a low-pressure transfer molding machine. Epoxy resin for semiconductor encapsulation (KE-300TS: manufactured by Toshiba Chemical Co., Ltd.)
The molding conditions (transfer molding) are temperature 175 ° C,
The test was performed at a pressure of 80 kg / cm ² for 3 minutes. Further, the sample thus obtained was left in a pressure cooker at 120 ° C. and 2.2 atm. Water vapor for 100 hours. For the sample subjected to the pressure cooker treatment (PCT) and the sample not subjected to the pressure cooker, the shear breaking strength of the 2 mm square silicon chip placed as described above was measured.

The results of the adhesion tests-A and B in Examples 5 to 8 are shown in Table 2 below.

As shown in Table 2, the polyimide film patterns formed by using the first photosensitive resin composition of the present invention are suitable as a protective film and an interlayer insulating film in a semiconductor device. It was confirmed that it had adhesiveness to the material and the sealing resin.

Synthesis Example 3 (Preparation of polyamide-amic acid resin varnish C) In a reaction flask equipped with a stir bar, a thermometer, and a dropping funnel, 10.65 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride ( 0.033 mol), 7.201 g (0.033 mol) of pyromellitic dianhydride, and 60 g of N-methyl-2-pyrrolidone were cooled to 0 ° C. with sufficient stirring. Subsequently, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 4
3.98 g (0.12 mol) and 2,92-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 2.92 g (0.0
06 mol) and 1.52 g (0.006 mol) of bis (γ-aminopropyl) tetramethyldisiloxane were added to N-methyl-2-
A solution dissolved in 120 g of pyrrolidone was gradually dropped using a dropping funnel. After the completion of dropping, the inside of the reaction flask is
The mixture was stirred for 3 hours while maintaining the temperature at 10 ° C. Next, a solution in which 13.42 g (0.066 mol) of isophthalic dichloride was dissolved in 30 g of tetrahydrofuran was gradually dropped using a dropping funnel. After completion of the dropwise addition, the mixture was stirred for 2 hours while maintaining the inside of the reaction flask at 10 ° C., and 7.2 g of propylene oxide (0.132
Mol). After that, stirring was continued for 8 hours to obtain a polyamide / amic acid resin as a resin component of the second photosensitive resin composition of the present invention in the form of a resin varnish. The intrinsic viscosity of the polymer was 0.52 dl / g (measured in N-methyl-2-pyrrolidone at a polymer concentration of 0.5 g / dl at 30 ° C.). This resin varnish is referred to as polyamide / amic acid resin varnish C.

Synthesis Example 4 (Preparation of Polyamide-Amidic Acid Resin Varnish D) In the following synthesis example, two reaction flasks of the same type as those used in Synthesis Example 3 above were used (reaction flasks 1 and 2 respectively). ) And synthesis of polyamide-amic acid resin.

First, 13.67 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride was added to the reaction flask 1.
(0.03078 mol), 21.982 g (0.06822 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and N-
80 g of methyl-2-pyrrolidone was charged and cooled to 0 ° C. with sufficient stirring. Then, in this suspension,
25.6537 g (0.07003 mol) of 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 10.5777 g (0.0210 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane , Bis (γ-aminopropyl) tetramethyldisiloxane 1.499 g (0.00
6 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone and 40 g of tetrahydrofuran, and gradually added dropwise using a dropping funnel. After the completion of the dropping, the reaction flask 1
The mixture was stirred for 2 hours while keeping the inside at 5 ° C.

On the other hand, 2,2-bis (3-amino-
4-hydroxyphenyl) hexafluoropropane 12.821
g (0.03497 mol) and 50 g of tetrahydrofuran were charged and cooled to 5 ° C. with sufficient stirring. Subsequently, 6.7188 g of isophthalic acid dichloride (0.033
Mol) was slowly added dropwise using a dropping funnel. After dropping, stirring was continued for 1 hour while maintaining the inside of the reaction flask 2 at 5 ° C., and then 3.8 g (0.066
Mol) was added and stirring continued for an additional hour.

Next, the reaction solution in the reaction flask 2 was poured into the reaction solution in the reaction flask 1, and stirring was continued at a temperature of 5 to 10 ° C. for 8 hours.
A polyamide / amic acid resin as a resin component of the second photosensitive resin composition of the present invention was obtained in the form of a resin varnish. The intrinsic viscosity of the polymer was 0.62 dl / g (N-methyl-2
-Polymer concentration in pyrrolidone 0.5 g / dl, measured at 30 ° C).
This resin varnish is referred to as polyamide / amic acid resin varnish D.

Example 9 1.0 g of a dissolution inhibitor d-1 was added to an acid generator b-1 to 50 g of the polyamide / amic acid resin varnish C prepared in Synthesis Example 3 above.
2.0 g, photosensitive agent c-1 2.5 g, and N-methyl-
10 g of 2-pyrrolidone was added to each, followed by sufficient stirring. Next, the reaction solution was filtered under pressure through a membrane filter having a hole diameter of 0.5 μm to prepare a second photosensitive resin composition of the present invention.

Examples 10 to 16 The second photosensitive resin composition of the present invention was prepared in the same manner as in Example 9 with the raw material compositions shown in Table 3 below.

Comparative Example 3 Dissolution inhibitor d-1 0.6 g and acid generator b-1 were added to 30 g of the polyamide-amic acid resin varnish C prepared in Synthesis Example 3 above.
1.0 g and 6 g of N-methyl-2-pyrrolidone were added, respectively.
Stir well. Next, the reaction solution was filtered under pressure through a membrane filter having a hole diameter of 0.5 μm to prepare a resin composition of a comparative example with respect to the second photosensitive resin composition of the present invention.

Comparative Example 4 To 30 g of the polyamide / amic acid resin varnish C prepared in Synthesis Example 3, 0.6 g of a dissolution inhibitor d-1 and a photosensitizer c-11.
2 g and 5 g of N-methyl-2-pyrrolidone were added respectively, and the mixture was sufficiently stirred. Next, the reaction solution was filtered under pressure through a membrane filter having a hole diameter of 0.5 μm to prepare a resin composition of a comparative example with respect to the second photosensitive resin composition of the present invention.

With respect to the second photosensitive resin composition of the present invention prepared as described above, the following characteristic tests were performed.

Pattern workability test (evaluation of resolution) The photosensitive resin compositions of Examples 9 to 16 and Comparative Examples 3 to
Using the resin composition of No. 4, a pattern was formed in the same manner as in the pattern workability test.

As a result, with respect to the photosensitive resin compositions of Examples 9 to 16, the non-exposed portions were hardly eroded by the developing solution, and good patterns were formed. In contrast, with respect to the resin compositions of Comparative Examples 3 and 4, all of the exposed and unexposed portions were dissolved by the developer. Further, with respect to the photosensitive resin compositions of Examples 9 to 16,
Further, heat treatment was performed in the same manner as in the pattern workability test. As a result, in any of the examples, there was no disturbance of the pattern formed before the heating and 3 to 5 μm.
The line width of m could be sufficiently identified.

Table 3 below shows the results of the above-mentioned characteristic tests for the photosensitive resin compositions of Examples 9 to 16 and Comparative Examples 3 and 4. It was confirmed that each of the polyimide film patterns formed by using the second photosensitive resin composition of the present invention had a resolution suitable for a protective film and an interlayer insulating film in a semiconductor device.

Adhesion Test-A '(Evaluation of Adhesion with Phosphosilicate Glass Film) For each of the photosensitive resin compositions of Examples 13 to 16, according to the same method as in the above-mentioned adhesion test-A, each photosensitive resin composition and phosphorus silicate were used. The adhesion with the acid glass film was evaluated.

Adhesion Test-B '(Evaluation of Adhesion with Epoxy Resin for Encapsulating Semiconductor) With respect to the photosensitive resin compositions of Examples 13 to 16, according to the same method as in the adhesion test-B, each photosensitive resin composition was used. The adhesion between the resin and the epoxy resin for semiconductor encapsulation was evaluated.

The results of the adhesion tests A 'and B' for the photosensitive resin compositions of Examples 13 to 16 are shown in Table 4 below.

As shown in Table 4, the polyimide film patterns formed using the second photosensitive resin composition of the present invention are suitable for use as a protective film and an interlayer insulating film in a semiconductor device. It was confirmed that it had adhesiveness to the material and the sealing resin.

〔The invention's effect〕

As described in detail above, the photosensitive resin composition of the present invention is:
The present invention has a remarkable effect in simplifying the process of forming a polyimide film pattern in a semiconductor device and in providing performance such as resolution and adhesion suitable as the film.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Naohiko Chisato 1 Toshiba, Komukai Toshiba-cho, Saisaki-ku, Kawasaki City, Kanagawa Prefecture (56) References JP-A-2-639 (JP, A) JP-A-63-96162 (JP, A) JP-A-64-6947 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (2)

(57) [Claims] 1. A polyamic acid having a copolymer structure containing (a) a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (I '): (b) an onium salt; At least one acid generator selected from the group consisting of organic halogen compounds, and (c) at least one photosensitive agent selected from the group consisting of orthoquinonediazidesulfonic acid ester and orthoquinonediazidosulfonic acid amide ester A photosensitive resin composition characterized in that: Here, R ^{1 to} R ³ indicate the following, respectively. R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group (A) a repeating unit represented by the following general formula (I), a repeating unit represented by the following general formula (I '), a repeating unit represented by the following general formula (II), General formula (I
(B) at least one acid generator selected from the group consisting of an onium salt and an organic halogen compound, and (c) a polyamide-amic acid having a copolymer structure containing a repeating unit represented by I ′); A) a photosensitive resin composition comprising at least one photosensitive agent selected from the group consisting of orthoquinonediazidesulfonic acid ester and orthoquinonediazidosulfonic acid amide ester; OCNH-R ¹ -NHCO-R ⁴ (II) OCNH-R ² -NHCO-R ⁴ (II ′) wherein R ^{1 to} R ⁴ represent the following, respectively. R ¹ : a divalent organic group having at least one phenolic hydroxyl group R ² : a divalent organic group not containing a phenolic hydroxyl group R ³ : a tetravalent organic group R ⁴ : a divalent organic group