KR950003824B1 - Photosesitive resin composition for forming polyimide film pattern and method of forming polyimide film pattern - Google Patents

Abstract

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Description

Photosensitive resin composition for forming polyimide film pattern and method of forming polyimide film pattern

1 is a graph showing photosensitivity in the photoexposure step of the photosensitive resin composition according to the present invention.

The present invention relates to a method for forming a photosensitive resin composition and a polyimide film pattern for forming a polyimide film pattern used as an inactive film, an α-ray shielding film or an intermediate film insulating film in an insulating material or semiconductor device which is an electronic component.

In a semiconductor device, a protective film (inactive film) is formed on the surface of a semiconductor support having a semiconductor device formed therein to protect the device from the influence of the external environment and to improve the reliability of the device.

In general, polyimide resins excellent in their electrical properties such as insulation and radiation resistance and heat resistance are widely used as protective film materials.

These excellent properties also enable the polyimide resin to be widely used as an interlayer insulating film material included in the α-ray shielding film material and the multilayer interconnect structure in semiconductor devices.

The polyimide resin film can be easily formed from the precursor of polyamic acid.

In particular, the predetermined surface is first applied with a glaze that is a polyamic acid and then heats the applied film to form a film.

Thereafter, heat treatment is applied to the membrane to cause the polyamic acid to cyclize.

As a result, the polyamic acid is cured (imidized) to form a polyimide film.

In this way, the stabilization treatment can be performed at a relatively low temperature, and as a result, the method is widely adopted.

Alternatively, pad machining or the like is required for the manufacture of semiconductor devices to make apertures in multi-layer interconnection structures or to make electrical connections to external lead wires.

As a result, it is essential to make a polyimide film formed as a protective film or an interlayer insulating film in a semiconductor device so as to form a hole having a predetermined pattern structure.

Generally, PEP (Photo Engraving Process) and polyimide film are employed to make photo resist.

In particular, a polyimide film is first formed on the surface of the semiconductor support having the semiconductor element formed therein, as described above, and forms a photoresist on the screw polyimide film.

Then, the photoresist is selectively exposed to light and subsequently developed to form a resist pattern.

Further, the polyimide film under the resist pattern is selectively corroded using the resist pattern as an etching resistant mask to form a polyimide protective film or an interlayer insulating film of a desired pattern.

In the conventional method of forming the polyimide film pattern described above, however, it is essential to form the polyamide film PEP for the pattern shape as two independent methods.

Naturally, the two step method makes handling polyimide film patterning difficult.

In order to overcome the above-mentioned difficulties, a resin composition containing a polyimide precursor is proposed, and it is possible for the composition to form a polyimide film not related to PEP.

For example, Japanese Patent Laid-Open No. 74-115541 discloses a reaction between diamine dichloride and diamine having a photopolymerizable group used in place of commonly used tetracarboxylic dianhydride induced by ester linkage. The polyimide acid ester manufactured by this is described.

Polyamic acid esters exhibit fusible photosensitivity.

In particular, upon exposure to light, the exposed portion of the composition itself is made to be insoluble in the developer.

Thereafter, the pattern can be made simultaneously with forming the polyamide film.

Alternatively, the polyimide film pattern may be formed without going through the photoacoustic method.

However, very unwieldy manipulations are required to synthesize compounds with photopolymerizable groups and to synthesize polymeric acid esters.

An additional difficulty is that chlorine ions are contained as impurities in the product resin.

In addition, the organic solvent is used as a developer, and as a result, it is essential to use a large amount of the organic solvent in the manufacturing method of the semiconductor device.

This is undesirable in view of stability, sanitation and environmental pollution.

It is also noted that the polyimide pattern formed is expanded by the solvent while having a low decomposition layer.

Japanese Patent Application Laid-Open No. 84-52822 describes a heat resistant photosensitive material (or negative photosensitive resin composition) containing an amino group and a compound having a carbon-to-carbon double bond that can be dimerized or polymerized by actinic radiation.

However, when the photosensitive material described in the prior art is used to form a protective film in a semiconductor device or the like of a resin-capsulated type, the protective film adheres to a semiconductor support, a protective film of inorganic material or a resin encapsulated on a support surface. Is low, and as a result, the reliability of the semiconductor device is reduced.

In addition, as in the case of using the aforementioned polyimide acid ester, it is essential to use an organic solvent as the developer in the developing step.

Thereafter, various problems arise as previously pointed out.

Japanese Patent Laid-Open No. 85-6365 describes a resin composition containing a compound prepared by adding aminomethacrylate as a salt to a carboxyl group which is a polyamic acid.

However, the photosensitive resin composition described in the prior art is defective in that the solubility of the solvent in which the composition is used is low.

In contrast, Japanese Patent Application No. 87-145240 describes a photosensitive resin composition containing a polymer having an isoimide structure.

The composition exhibits positive photosensitivity.

In particular, upon exposure to light, the exposed portion of the composition may be dissolved in the developing solution. However, the polymer is low in heat resistance and photosensitivity and makes it impossible to use a composition for forming a protective film included in a semiconductor device.

Photosensitive resin compositions exhibiting positive photosensitivity are also described in Japanese Patent Laid-Open No. 89-60630.

In particular, compounds prepared by the addition of photosensitizers, which are O-quinone diazide compounds, to amides that are dissolved in a solvent are described in the prior art, wherein the imide is formed between a diamine and an acid anhydride having a hydroxyl group bonded to an aromatic ring. Synthesized by reaction.

Further, Japanese Patent Laid-Open No. 87-135824 describes a similar photosensitive resin composition containing a photosensitive quinoquinone diazide.

Moreover, Japanese Patent Laid-Open No. 85-37550 describes a polyimide photosensitive precursor having an O-nitrobenzyl ester group.

The aqueous alkali solution can be used for the development of the positive photosensitive resin composition.

The problems caused by the use of organic solvents need not be worried.

However, the composition of the polymer, which is the main component of the resin composition, is limited to the case of the positive photosensitive resin composition, causing low adhesion with silicon wafers, glass supports, ceramic supports, encapsulated resins, metals, and the like, which are widely used in semiconductor devices.

Additionally, Japanese Patent Laid-Open Publication No. 77-13315 can be developed with a photosensitive precursor of an aqueous alkali solution, i.e., a polyimide, which uses a solubility in an alkaline solution which is a polymeric acid and uses a naphthoquinone diazide compound as a decomposition inhibitor. A positive photosensitive resin composition is described.

Polyimide photosensitive precursors enable pattern formation with methods of simplifying film formation, exposure and development.

However, the difference in solubility in alkaline developer is not very large between exposed and non-exposed portions and makes it difficult to form fine polyimide film patterns.

In addition, Japanese Patent Laid-Open Publication No. 87-135824, which is previously referred to, describes that the photosensitive polyimide precursor film is heated to about 90 ° C. before being exposed to light in order to improve the resolution of the formed polyimide film pattern.

Even if a special method is applied, however, the resolution is not sufficient when using the photosensitive precursor of the polyimide noted above.

It is an object of the present invention to simplify the method of forming the preformed polyimide film pattern.

More specifically, the present invention provides a photosensitive resin composition and a method of forming a polyimide film pattern for forming a polyimide film pattern without using a photoresist.

A photosensitive resin composition is provided for forming a polyimide film pattern according to the first embodiment of the present invention, and is composed of a polyimide acid derivative and a photoreceptor having a repeating unit represented by the following general formula (1):

(Wherein, R ¹ is Saga organic group, R ² is a divalent represents an organic group, R ³ and R ⁴ is a monovalent organic group or hydroxyl, R ³ and R ⁴ at least one of the at least one bond to an aromatic ring It is an organic group having a hydroxyl group.)

According to a second embodiment of the present invention, there is provided a photosensitive resin composition for forming a polyimide film pattern, wherein the composition is a polyimide acid derivative having a repeating unit represented by the following general formula (I), It consists of a polyimide acid and a photoreceptor with repeating units indicated by:

Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group, R ³ and R ⁴ represent a monovalent organic group or a hydroxyl group, and at least one of R ³ and R ⁴ is bonded to an aromatic ring An organic group having at least one hydroxyl group, R ⁵ represents a tetravalent organic group, and R ⁶ represents an organic group.)

Further, according to a third embodiment of the present invention, there is provided a photosensitive resin composition for forming a polyimide film pattern, wherein the photosensitive resin composition is a repeating unit represented by the following general formula (1) and the following general formula (2) It consists of a polyimide acid derivative and a photoreceptor having a polymer structure comprising a repeating unit represented by:

Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group, R ³ and R ⁴ represent a monovalent organic group or a hydroxyl group, and at least one of R ³ and R ⁴ is bonded to an aromatic ring An organic group having at least one hydroxyl group, R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group.)

Moreover, the present invention provides a method of forming a polyimide film pattern, and consists of the following steps:

As a main component, a resin layer containing a polyimide acid and a naphthoquinone diazide compound having a repeating unit represented by the following general formula (2) was formed on a support as a main component:

(Wherein R ⁵ represents a tetravalent organic group and R ⁶ represents a divalent organic group.)

Optionally exposing a predetermined region of the resin layer to light; Calcining is applied to the resin layer at 130 to 200 캜 after light exposure; Developing the resin layer to optionally remove or leave the preliminary region of the resin layer after the firing treatment; The method of forming a polyimide membrane pattern is comprised by heating the developed resin layer in order to amidate a resin layer.

Additional objects and advantages of the invention will appear from the accompanying description and become apparent in part from the description, or may be learned by practice of the invention.

The objects and advantages of the invention may be realized or obtained by means and combinations particularly pointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and the general description given above and the following detailed description of the preferred embodiments illustrate the principles of the invention.

In the present invention, the support surface is first applied with the photosensitive resin composition according to any one of the first to third embodiments of the present invention, then exposing the resin composition layer to light through a mask having a predetermined pattern, and then the resin It is developed to form a composition layer. Finally, the patterned composition layer is heat treated to form a preferred polyimide film pattern.

The photosensitive resin composition according to any one of the first to third embodiments of the present invention is composed of a resin component non-photosensitive component.

The resin composition contained in the photosensitive resin composition according to the first embodiment of the present invention is a polyimide acid derivative having a repeating unit represented by the general formula (1) given above.

Polyimide acid derivatives, precursors of polyimides, can be synthesized by either of the two methods described below.

In the first method, the compound represented by formula (4) given below is an alcoholic compound having tetracarboxylic dianhydride represented by formula (3) given below and at least one hydroxyl group directly bonded to an aromatic ring. Is formed in the first step by reaction between any one of amine compounds and alkoxides:

(Wherein R ¹ , R ³ and R ⁴ are as described in general formula (1) above)

In this step, the molar ratio of tetracarboxylic dianhydride to additive must be fixed at about 1: 1 to 1: 2.

In a second step, it is carried out in an organic solvent in the diamine and dehydrating agent represented by the general formula (4), the following general formula (5):

NH ₂ -R ² -NH ₂ . … … … … … … … … … … … … … … … … … … … (5)

(Wherein R ² is the same as described in the general formula (1).)

In this state, the molar ratio of the reactants should be fixed at about 1: 1: 2 (or at least 2).

As a result, the polyimide acid derivative having a repeating unit surfaced by the general formula (1) is a polyimidization of the compound represented by the general formula (4) and the diamine represented by the general formula (5). Synthesized by

The tetracarboxylic dianhydride represented by the general formula (3) used in the first step reaction is not particularly limited in the present invention.

In particular, tetracarboxylic dianhydrides used in the present invention are for example pyromellitic dianhydrides (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 1,4 , 5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3, 3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [5- (3,4-dicarboxyphenoxy) Phenyl] propane dianhydride, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4- Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-3,4,9,10-tetracarboxyl Water, butane tetracarboxylic dianhydride, 2,2 '-(3,4-dicarboxyphenyl) hexafluoro propane dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, and bis (3, 4-dicarboxyphenyl) tetramethyl-disiloxane dianhydride. The tetracarboxylic dianhydrides may be used singly or in combination.

In a first step, the reaction is carried out between the tetracarboxylic dianhydride given above and the alcohol compound, amine compound, phenol compound or alkoxide given below. More specifically, the alcohol compound used in the first stage reaction is represented by the general formula (6) given below:

R ⁷ -OH... … … … … … … … … … … … … … … … … … … … (6)

(Wherein R ⁷ -O-same as R ³ or R ⁴ predefined).

In the general formula (6), R ⁷ − represents an organic group having at least one hydroxyl group bonded to an aromatic ring.

Particular alcohol compounds used in the present invention are, for example, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxyphenylethyl alcohol, 3-hydroxyphenylethyl alcohol, 4-hydroxyphenylethyl alcohol, 4-hydroxyphenyl-3-propanol, 4-hydroxyphenyl-4-butanol and hydroxynaphthylethyl alcohol.

In the present invention, it is particularly preferable to use an alcohol compound represented by the following general formula (7):

(Wherein p is a positive integer, preferably 1-4)

The amine compound used in the first stage reaction is the primary or secondary amine represented by the following general formula (8):

R ⁸ -N (R ⁹ ) H... … … … … … … … … … … … … … … … … … … … (8)

(Wherein R ⁸ -N (R ⁹ ) has the same predefined R ³ or R ⁴ , and R ⁹ represents hydrogen or monovalent organic group.)

R ⁸ − included in formula (8) given above represents an organic group having at least one hydroxyl group bonded to an aromatic ring.

Particular amine compounds used in the present invention are, for example, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-4'-hydroxy diphenylethane, 4-amino-4'-hydroxy Sidiphenyl ether, 2- (4'-aminophenyl) -2- (3'-hydroxyphenyl) propane, 2- (4'-aminophenyl) -2- (3'-hydroxyphenyl) hexafluoropropane , 2- (3'-aminophenyl) -2- (3'-hydroxyphenyl) propane, 2- (4'-aminophenyl) -2- (4'-hydroxyphenyl) propane and 2- (4 ' -Aminophenyl) -2- (4'-hydroxyphenyl) hexafluoropropane.

Particular preference is given to primary or secondary amines represented by the general formula (9) given below:

(Wherein R ⁹ represents hydrogen or a monovalent organic group and q is a positive integer, preferably 0 to 4)

The alkoxide used in the first stage reaction is provided by, for example, sodium alkoxide or potassium alkoxide, which is an alcohol compound represented by the general formula (6) described above.

In the reaction between any one of the first step, tetracarboxylic dianhydride and alkoxy compound, the amine compound and alkoxide described above are carried out at room temperature or at about 25 to 200 ° C.

The solvent may or may not be used for the reaction.

In addition, the catalyst may or may not be used in the reaction.

When using the alcohol compound represented by the general formula (6), the primary or secondary amine represented by the general formula (8) or the above-mentioned alkoxide in the first step reaction, represented by the general formula (10) given below And the compounds included in Formula (4) previously described are prepared:

(Wherein X ^* is -O- or -N- (R ⁹ )-, R ^* is a predefined R ⁷ , R ⁸ or hydrogen, at least one of the two R ^* groups is not hydrogen.)

Alternatively, the diamine represented by the general formula (5) used in the second stage reaction is not particularly limited.

Particular diamines used in the present invention are, for example, aromatic diamines, such as m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3'-diaminodiphenylether, 4,4 '. -Diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminophenylsulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diamino-diphenyl sulfone , 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl-methane, 4,4'-diaminodiphenyl sulfide, 3,3 ' -Diamino-diphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4 -Aminophenyl) hexafluoropropane, 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-pentane, 1,4-bis (a, a -Dimethyl-4-aminobenzyl) benzene, already -Di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diamino-naphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino -(4-aminophenyl) -1,3,3-trimethyllindane, bis (p-aminophenyl) phosphine oxide, 4,4'-diamino azobenzene, 4,4'-diaminodiphenylurea, 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] benzopinone, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 4,4'-bis [ 4-a, a-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [4- (a, a-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, bis (4 -Aminophenyl) dimethylsilane and bis (4-aminophenyl) tetramethylsiloxane.

It is also possible to use derivatives of these aromatic diamines in which at least one substituent selected from the group consisting of chlorine, fluorine, bromine, methyl, methoxy, cyano and phenyl is substituted with a hydrogen atom bonded to an aromatic ring which is an aromatic diamine.

Moreover, 3,5-diamino-1-hydroxybenzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diamino Biphenyl, 2,2-bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2- (3-hydroxy-4-aminophenyl)-(2- (3-amino-4-hydroxyphenyl) hexafluoro Propane, bis (p-aminophenyl) tetramethyl disiloxane, bis (γ-aminopropyl) tetramethyl disiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyl Disiloxane, bis (γ-aminopropyl) tetraphenyl disiloxane, 4,4'-diamino-biphenyl, phenylindan diamine, 3,3'-di Oxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, bis (4-aminophenoxyphenyl) sulfone, bis (4-amino Phenoxyphenyl) sulfide, 1,4-bis (4-aminophenoxyphenyl) benzene, 1,3-bis (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) anthracene (10 ), 9,9-bis (4-aminophenyl) fluorene, 4,4'-di- (3-aminophenoxy) diphenyl sulfone, 4,4'-diaminobenz amylide and the general formula given below

(Wherein l is 2 to 12 integers).

The diamines may be used singly or in combination.

The dehydrating agents used in the second stage reaction are, for example, sulfuric acid, hydrochloric acid, p-toluene sulfonic acid, cobalt acetate, manganese acetate, tin chloride, ditin chloride, polyphosphate, triphenyl phosphite, bis-o-phenylene , Phosphate, N, N '-(phenylphosphino) bis [2 (3H) -benzothizolone], a carbodiimide derivative represented by the general formula RN = C = NR ¹ and preferably dicyclohexyl carboy Mead (DCC).

In general, since non-strongly acidic polar solvents are suitable in polymer synthesis, they are used as organic solvents in the synthesis of resin components having repeating units represented by the general formula (1).

In the synthesis of polyimide acid derivatives used in the present invention, it is also possible to use aromatic hydrocarbons, tetrahydrofuran, dioxane and the like as solvents.

Solvents which are particular compounds used in the present invention include, for example, ketone-based solvents such as cyclohexanone acetone, methylethyl ketone and methyl isobutyl ketone; Contract solvents such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate; Ester solvents such as ethyl acetate, butyl acetate and isoamyl acetate; Ether series solvents such as tetrahydrofuran and dioxane; Other solvents such as N, N-dimethyl formamide, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, γ-carrolactone, sulfolane, N , N, N ', N'-tetramethylurea, hexamethylphosphoamide, toluene and xylene.

The solvents may be used singly or in combination.

The second stage reaction can be carried out under cooling or heating.

That is, at a falling temperature in the range of −20-100 ° C., for about 30 minutes to 24 hours, preferably about 1 to 8 hours, more suitably 4 to 8 hours.

In a first method of synthesizing a polyimide acid derivative having a repeating unit represented by formula (1), a monomer having a substituent derived from a carboxylic acid (alcohol compound, amine compound or alkoxide described above) (carboxylic acid Derivatives) are formed in the first stage reaction.

Then, in the second stage reaction, the polymer chain (polyamic acid derivative) with substituents induced by the side chain is formed by the polycondensation reaction between the monomer formed in the first stage reaction and the diamine described above.

In summary, the first method of synthesizing polyimide acid derivatives is characterized in that the substitution is followed by a polymerization sequence.

In a second method of synthesizing a polyimide acid derivative having a repeating unit represented by formula (1), which is a resin component of the photosensitive resin composition according to the first embodiment of the present invention, the polymerization reaction is carried out in formula (3). It is carried out in the first step between the tetracarboxylic dianhydride represented by and the diamine represented by the general formula (5).

The molar ratio of tetracarboxylic dianhydride to diamine should be fixed at about 1.1: 1.0 to 1.0: 1.1 preferably 1.0: 1.0.

As a result, a polyimide acid having a repeating unit represented by the general formula (11) represented below is formed:

In the second step, the organic in the polyimide acid, alcohol compound, amine compound or alkoxide having at least one hydroxyl group directly bonded to the aforementioned aromatic ring having the repeating unit represented by general formula (II) mentioned above In solvent and dehydrating agent.

In this step, the molar ratio of the reactants is a molar amount of polyimide acid having a repeating unit represented by the general formula (11) calculated in the concept of about 1: 1: 1 to 1: 2: 2 tetracarboxylic acid unit). It must be fixed as.

In this step, a dehydration condensation reaction occurs between the polyimide acid and the alcohol compound, the amine compound or the alkoxide having the repeating unit represented by the general formula (11).

As a result, the substituent is introduced into the side chain (carboxyl group) of the repeating unit 11 to form a polyimide acid derivative having a repeating unit represented by the general formula (1).

Any kind of the tetracarboxylic dianhydride represented by the general formula (3) and the diamine represented by the general formula (5) can be used for the first step reaction of the second method up to these tetracarboxylic dianhydrides and the diamine is described in advance. It can be used in the first method for synthesizing the polyimide acid derivative.

In the first step of the second method, the polymerization reaction can be carried out by any of a solution polymerization method, an interfacial polymerization method and a melt polymerization method.

Organic solvents that can be used in the first method of synthesizing polyimide acid derivatives can also be used as solvents in the solution polymerization method.

In the case of using the solution polymerization method in the first step of the second method, the reaction temperature must be fixed at -60 to 150 ° C.

If the reaction temperature is less than -60 ℃, the reaction rate is very low.

In this case, it is essential to carry out the polymerization reaction for a long time.

This is not suitable for industrial production of polyimide acid derivatives.

When the reaction temperature exceeds 150 ° C., however, side reactions tend to occur.

In addition, traces of water contained as impurities in the reaction system give rise to the hydrolysis of the product polyimide acid with the repeating unit represented by the general formula (11).

Preferred polymerization reactions are suppressed and the molecular weight of the resultant polyimide acid having a repeating unit represented by the general formula (11) is reduced.

Preferably, solution polymerization is carried out at falling temperatures in the range of -20 ° C-60 ° C.

In the case of adopting the solution polymerization reaction method in the first step, the reaction should be carried out for 30 minutes to 24 hours, preferably 1 to 8 hours.

If the reaction time is 30 minutes or less, the polymerization reaction can proceed sufficiently.

If the reaction time exceeds 24 hours, however, no industrial advantage can be obtained.

Preferably, the reaction should be carried out for 1 to 8 hours.

More preferably, it should be carried out for 4 to 6 hours to avoid the above mentioned difficulties, ie hydrolysis and undesirable side reactions of polyimide acids having repeating units represented by formula (11) caused by impurities do.

In the second step reaction included in the second synthesis method described above, a polyimide acid derivative related to any of an alcohol compound, an amine compound and an alkoxide having at least one hydroxyl group bonded to an aromatic ring, a dehydrating agent and an organic solvent is synthesized. It is possible to use compounds which can be used in the first method.

In the second stage reaction, the amount of any of alcoholic compounds, amine compounds and alkoxides depends on the reactivity of the specific compound used against one mole of tetracarboxylic dianhydride represented by formula (3) used in the first stage reaction. It is determined to descend within the range of 1 mol-4 mol.

By appropriately controlling the amount of the above-mentioned alcoholic compound or the like according to the object, the amount of the substituent derived from the side chain of the product polyimide derivative represented by the general formula (1), that is, R ³ and R ⁴ It is possible to control the rate of introduction and the use of the final photosensitive resin composition.

For example, when the photosensitive resin composition is used to form a polyimide film pattern by lithography technique, it is essential that the composition can be dissolved in an alkaline solution.

In this case, it is necessary to fix the amount of the additive in a smaller amount compared to 2 moles or 1 mole of tetracarboxylic dianhydride represented by the general formula (3).

The second stage reaction is carried out for 30 minutes to 24 hours, cooling or heating, i.e., a temperature falling within the range of -60-200 ° C.

If the reaction temperature is below -60 ° C, the reactivity of the dehydration condensation reaction is clearly lowered.

If the reaction temperature exceeds 200 ° C., however, side reactions such as decomposition and gelation of the main chain of the reactive polyamic acid having the repeating unit represented by the general formula (11) tend to occur easily.

The second stage reaction should be carried out at -60 to 100 ° C for about 1 to 8 hours and more preferably at -20 to 50 ° C for about 4 hours.

As described above, the second method of synthesizing a polyimide acid derivative having a repeating unit represented by formula (1) is a first step reaction for forming a polymer chain (polyamic acid) and a preferred polyimide acid derivative. It consists of a second step reaction to introduce substituents (alcohols, amines and alkoxides) into the polymer side chain for synthesis.

Finally, the second method is characterized in that it is polymerized and then proceeds in the order of introduction of the opposite substituents in the first method.

In the second method, the polymerization reaction rate carried out in the first step is promoted because the polymerization reaction carried out between the acid anhydride and the diamine is carried out quantitatively.

The resulting polymer makes it possible to have sufficiently large molecular weights.

In the first method, however, the condensation reaction involving the dehydrating agent does not necessarily proceed in quantity to the polymerization reaction carried out in the second step.

In addition, since the substituent group is already bonded to the monomer, the monomer molecule becomes bulky depending on the type of the substituent group.

Thereafter, the polymerization reaction rate tends to be small.

Alternatively, the degree of polymerization of the polymer formed tends to be lower in some cases.

In the second method, however, the polymer formed by the side reactions generated by the dehydrating agent is partially gelled.

As a result, there exists a tendency for the decomposition force to become low in the polyimide membrane pattern formed by using the photosensitive resin composition containing the said polymer.

Under the above conditions, in the case of forming a fine polyimide film pattern of 10 microns or less, it is preferable to synthesize the polyimide acid derivative by the first method.

Alternatively, the polyimide film pattern formed by using the photosensitive resin composition containing the polymer synthesized by the second method is excellent in its mechanical strength.

While it is required that the polyimide film pattern exhibit high mechanical strength, it is possible to adopt the second method for synthesizing the polyimide acid derivative.

In the present invention, the additional compound given below is a compound for inducing a substituent group in the side chain of a polyimide acid derivative having a repeating unit represented by formula (1), that is, by the formula (3) It can also be used as a compound which reacts with the represented tetracarboxylic dianhydride or as a compound which reacts with the polyamic acid represented by the general formula (11) in the second step of the second method.

In particular, alcohol compounds having no hydroxyl group bonded to the aromatic ring, amine compounds having no hydroxyl group bonded to the aromatic ring, alkoxides and alkoxy compounds having no hydroxyl group bound to the aromatic ring, amine compounds and aromatics It is possible to use with these compounds any of the phenolic compounds having only one hydroxyl group bonded to the aromatic ring bonded together with an alkoxide having at least one hydroxyl group bonded to the ring.

Alcohol compounds having no hydroxyl group bonded to the aromatic ring include, for example, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, methylbenzyl alcohol, cinnamil alcohol, methoxybenzyl alcohol, allyl alcohol, crotyl alcohol and 2-hydroxyethyl methacrylate.

Amine compounds having no hydroxyl group bonded to the aromatic ring include, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, aniline, toluidine ethyl aniline and benzylamine.

Alkoxides having no hydroxyl group bonded to an aromatic ring include, for example, sodium alkoxides and potassium alkoxides of the abovementioned alcohols.

In addition, the aforementioned phenols include, for example, phenol, cresol, xylenol, butylphenol, allyl phenol and methoxy phenol.

When using a compound having no hydroxyl group bound to the above-mentioned aromatic ring or special phenolic compound, the amount of the special compound is based on the total amount of the compound used to introduce a substituent group into the side chain of the polyimide acid derivative. Should be about 80 mole% / or less.

If the above-mentioned amount is larger than 80 mol%, the solubility of the photosensitive resin composition in the developing solution is lowered, causing a low resolution of the polyimide film pattern formed by using the composition.

More preferably, the amount of specific compounds should be no greater than 60 mole percent.

In this case, the above-mentioned special polyimide acid derivatives and polyimide acid derivatives having an organic group in which a hydroxyl group is introduced into a side chain bonded to an aromatic ring are used to form a mixture in the resin component which is the photosensitive resin composition of the present invention. It is possible.

It is also possible for these two kinds of polyimide acid derivatives to form copolymers.

The polyimide acid derivative which has a reaction unit represented by General formula (1) is refine | purified as follows.

In the first step, methanol, ethanol, water and the like used in an amount of about 1 to 2 moles per mole of dehydrating agent are added to the reaction solution of the polyimide acid derivative and the system reacts with the unreacted dehydrating agent to form a precipitate. Stir for time.

The precipitate is then removed out of the system by filtration.

The prepared reaction solution is added to methanol, ethanol or water in an amount of 5 to 100 times as much as the reaction solution to precipitate the polymer as a result.

In addition, the washed polymer is dried under vacuum at 60 ° C. to separate and purify the polyimide acid derivative.

In the photosensitive resin composition according to the second embodiment of the present invention, the resin component is composed of a polyamic acid having a repeating unit represented by the general formula (1) given above and the repeating unit represented by the general formula (2) given above. Provided by the mixture.

The polyimide acid derivative having a repeating unit represented by formula (1) may be synthesized as in the polyimide acid derivative contained in the photosensitive resin composition according to the first embodiment of the present invention.

In addition, the above-mentioned polyimide acid derivatives may be synthesized by using compounds similar to those used in the first embodiment of the present invention described above.

Alternatively, polyamic acids having repeating units represented by formula (2) can be synthesized by either of the two methods described below.

In the first method, the tetracarboxylic dianhydride represented by formula (12) given below and the diamine represented by formula (13) given below are carried out in a suitable solvent.

The reaction should be carried out at -20-20 ° C, preferably -5-10 ° C, to obtain a polyamic acid having a repeating unit represented by the following general formula (2):

Here, R ⁵ and R ⁶ are as already defined in general formula (2).

In the first method, tetracarboxylic dianhydride represented by general formula (3), tetracarboxylic dianhydride (12) represented by diamine general formula (12) represented by general formula (5), general formula ( Tetracarboxylic dianhydride (12) represented by 13), diamine represented by formula (13), and a solvent, respectively, used for the synthesis of polyimide acid derivatives having repeating units represented by formula (1). It is possible to use compounds similar to solvents.

In the second method, the monoamine represented by the general formula (14) given below and the dicarboxyl anhydride represented by the general formula (15) given below are represented by the general formula (12) in the presence of an organic solvent. Anhydrides react with tetracarboxylic dianhydride represented by formula (12) and diamine represented by formula (13) in the presence of an organic solvent.

In this case, multiple reactions are carried out in an organic solvent to obtain a polyamic acid having a repeating unit represented by formula (2).

H ₂ NA... … … … … … … … … … … … … … … … … … … (14)

Here, A represents a monovalent organic group.

Here, B represents a divalent organic group.

In the polycondensation reaction carried out in the second method, using a monoamine represented by the general formula (14), a tetracarboxylic dianhydride represented by the general formula (12) and a diamine represented by the general formula (13) In the case, a polyamic acid represented by the general formula (16) given below is synthesized as a polyamic acid having a repeating unit represented by the general formula (2):

Here, r represents a positive integer.

Alternatively, in the polycondensation reaction carried out in the second method, the dicarboxylic anhydride represented by the general formula (15), the tetracarboxylic dianhydride represented by the general formula (12) and the diamine represented by the general formula (13) When using, polyamic acid represented by the general formula (17) given below is synthesized into a polyamic acid having a repeating unit represented by the general formula (2):

Monoamines represented by formula (14) are, for example, m-aminodiphenyl, P-amino diphenyl, m-aminodiphenyl ether, p-aminodiphenyl ether, aniline, o-anisidine,- Anidine, p-anisidine, p-aminobenzaldehyde, o-toluidine, m-toluidine and p-toluidine.

Dicarboxylic anhydrides represented by formula (15) include, for example, phthalic anhydride, hexahydrophthal anhydride, methylnadicanehydride 4-methylhexahydrophthal anhydride, methyltetrahydrophthal anhydride and male anhydride. do.

When adopting the second method for the synthesis of polyamic acid having a repeating unit represented by formula (2), it is used for the synthesis of polyimide acid derivatives having the repeating unit represented by formula (1). Respective compounds similar to the tetracarboxylic dianhydride represented by the general formula (3) and the diamine compounds represented by the general formula (5) are represented by the tetracarboxylic dianhydride and the general formula represented by the general formula (12), respectively. It is possible to use with the diamine represented by (13).

In particular, since the use of the siloxane compound improves the adhesive force between the finally obtained polyimide film and the semiconductor support, it is preferable in the present invention to use siloxane as the diamine represented by the general formula (13).

The organic solvent used in the polycondensation reaction used in the second method of synthesizing polyamic acid having a repeating unit represented by formula (2) is, for example, N, N-dimethyl-formamide, N, N- Dimethylacetoamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, γ-butylolactone, sulfolane, N, N, N ', N'-tetramethylurea and hexamethyl phospho Amides.

In a second method of synthesizing a polyamic acid having a repeating unit represented by formula (2), the sum of the monoamine represented by formula (14) and the diamine represented by formula (13) as follows: It is essential to fix the ratio of the dicarboxylic dianhydride represented by the general formula (15) and the tetracarboxylic dianhydride represented by the general formula (12).

In particular, amino group (-NH ₂ ) vs. acid anhydride group The equivalence ratio of should be about 100: 100.

In addition, in the second method, the reaction must be carried out at -15 to 30 ° C for 10 minutes to 20 hours.

In order to improve the coating ability of the photosensitive resin composition or polyamic acid on the surface of the semiconductor support, N-methyl-2-pyrrolidone of 0.4 to 1.0 dl / g, preferably 0.5 to 0.9 dl / g, maintained at 30 ° C When measured under a polymer concentration of 0.5 g / dl in a solvent, it is preferred that the resulting polyamic acid having a repeating unit represented by formula (2) has logarithmic viscosity.

In the second method of synthesizing a polyamic acid having a repeating unit represented by the general formula (2), the logarithmic viscosity of the polyamic acid having a repeating unit represented by the general formula (2) is lowered within the above-mentioned range In order to control the mixing ratio of the raw materials as described below is essential.

Formula (16) by using polycondensation reactions in monoamines represented by formula (14), tetracarboxylic dianhydrides represented by formula (12) and diamines represented by formula (13) In synthesizing the polyamic acid represented by the following, the molar ratio of monoamine (14) to diamine (13) should be 0.01-0.2: 0.9-0.995, preferably 0.02-0.06: 0.97-0.99.

If the mixing amount of the monoamine 14 is unreasonably large, the logarithmic viscosity of the synthesized polyamic acid 16 becomes small, with the disadvantageous result of obtaining a cured film having a smooth surface.

Alternatively, if the mixing amount of the monoamine 14 is unreasonably small, it is impossible to sufficiently obtain the effect of treating the molecular ends of the polyamic acid 16, with difficulty in working capacity.

Dicarboxylic anhydride when synthesize | combining the polyamic acid represented by General formula (17) using the polycondensation reaction in dicarboxylic anhydride (15), tetracarboxylic dianhydride (12), and diamine (13). The molar ratio of (15) and tetracarboxylic dianhydride (12) should be 0.01-0.2: 0.9-0.995, preferably 0.02-0.06: 0.97-0.99.

If the mixing amount of the dicarboxylic anhydride 15 is unreasonably large, the logarithmic viscosity of the synthesized polyamic acid 17 is lowered, causing a disadvantage that the cured film has a smooth surface.

On the other hand, if the mixing amount of the dicarboxylic anhydride 15 is unduly small, it is impossible to sufficiently obtain the effect in the molecular terminal treatment of the polyamic acid (7) if difficulty arises in view of workability.

When preparing the siloxane compound as the diamine 13 in the synthesis of the polyamic acid (16) or (17), the siloxane compound is added in an amount of 0.01-20 mol% based on the total amount of the amine compound (monoamine is calculated in terms of the diamine). It is desirable to use new compounds.

If the amount of the siloxane compound mixed exceeds 20 mol%, the heat resistance of the final polyimide film tends to be lowered.

Alternatively, if the amount of the siloxane compound mixed is smaller than 0.01 mol%, it is impossible to obtain an effect of improving the adhesive force between the polyimide film and the semiconductor support.

In the present invention, since the second method stably synthesizes a polyamic acid which is a preferred chemical support, the monoamines (14) and the dicar are used to synthesize the polyamic acid having a repeating unit represented by the general formula (2). It is preferable to adopt the second method of using the compound anhydride 15.

The photosensitive resin composition according to the second embodiment of the present invention is both a polyimide acid derivative having a repeating unit represented by formula (1) and a polyamic acid having a repeating unit represented by formula (2) as a resin component. It contains.

The mixing amount of the polyamic acid derivative should be 20-98 parts by weight, preferably 30-95 parts by weight, based on 100 parts by weight of the total amount of the resin component.

If the mixing amount of the polyamic acid derivative is smaller than 20 parts by weight, the decomposition rate in the developing solution is the light-exposed portion and the unexposed portion in the case of forming the polyimide film formed by using the photosensitive resin composition of the present invention by ore plate printing or the like. Increase in both.

Thereafter, the preferred pore contrast becomes small.

It should also be noted that polyamic acid improves the mechanical strength of the final polyimide membrane.

In order to fully obtain the effect of improving the mechanical strength, it is essential to use at least 20 parts by weight of polyamic acid.

As in the photosensitive resin composition according to the first embodiment of the present invention, the photosensitive resin composition according to the second embodiment of the present invention has a polyimide acid derivative having a substituent which does not have a hydroxyl group bonded to the aromatic ring induced by the side chain. It is possible to contain.

The photosensitive resin composition according to the third embodiment of the present invention is a resin having a copolymer structure comprising a repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) given above as a resin component. It contains a carboxylic acid derivative.

It is possible to synthesize polyamic acid derivatives having a copolymer structure by a method similar to the first method of synthesizing polyamic acid derivatives contained in the photosensitive resin composition according to the first embodiment of the present invention.

In particular, in the first step, an alcohol compound having at least one hydroxyl group bonded to an aromatic ring, to obtain a compound represented by the general formula (4) of tetracarboxylic dianhydride (3), at least bonded to an aromatic ring An amine compound having one hydroxyl group and an alkoxide having at least one hydroxyl group bonded to an aromatic ring.

The molar ratio of tetracarboxylic dianhydride to additive must be fixed at 1: 1 to 1: 2.

The reaction is carried out in the presence or absence of a solvent at room temperature or under heating.

In the second step, the reaction in compound (4), diamine (5) and dehydrating agent is carried out in an organic solvent.

The molar ratio of the reactants should be set to S: (s + t): 2s (s and t are positive integers) or higher.

The reaction is carried out under cooling or heating conditions for about 1 to 8 hours, preferably for at least 4 hours.

Further, in the third step, tmol of tetracarboxylic dianhydride (3) is prepared in the reaction solution prepared in the second step to carry out the reaction for 1 to 8 hours, preferably at least 4 hours at 0 to 20 ° C.

As a result, derivatives of polyamide acid and copolymer structures having repeating units are prepared by two general formulas (1) and (2).

In this case, R ¹ and R ⁴ included in the general formulas (1) and (2) correspond to R ⁵ and R ⁶ , respectively.

In the second step, compound (4) does not fully react with the diamine depending on the kind of dehydrating agent used.

In some cases, unreacted diamine 5 remains in the reaction product, even though t moles of tetracarboxylic dianhydride 3 are added in the third step.

If unreacted diamine remains in the photosensitive resin composition, the safety tends to be reduced in relation to the photosensitizer, in particular the o-quinone diazide compound, which will be described later.

In order to reduce the amount of unreacted diamine remaining, it is possible to add at least t moles of tetracarboxylic dianhydride in the third step.

Alternatively, an equivalent reaction between compound (4) and diamine (5) is carried out in the second step, followed by addition of excess tetracarboxylic dianhydride (3) in the third step to treat the unreacted diamine.

It is possible to increase the molecular weight of the resin component by reacting the tetracarboxylic dianhydride (3) with the unreacted reactant.

In the resin component synthesis contained in the photosensitive resin composition according to the third embodiment of the present invention, tetracarboxylic dianhydride (3), an alcohol compound having at least one hydroxyl group bonded to an aromatic ring, at least bonded to an aromatic ring The first and second aspects of the invention in connection with any one of an amine compound having one hydroxyl group, an aromatic ring, a diamine (5), a dehydrating agent and an alkoxide having at least one hydroxyl group bonded to any one of solvents. It is possible to use any of the compounds used for the synthesis of the resin component contained in the photosensitive resin composition according to the embodiment.

In synthesizing the resin compound contained in the photosensitive resin composition according to the third embodiment of the present invention, an alcohol compound having no hydroxyl group bonded to an aromatic ring, an amine compound having no hydroxyl group bonded to an aromatic ring, and a bonding to an aromatic ring An alkoxide having no hydroxyl group, or at least one hydroxyl bound to an aromatic ring together with at least one hydroxyl group bound to an aromatic ring, an amine compound having at least one hydroxyl group bonded to an aromatic ring It is possible to use alkoxides having at least one hydroxyl group bonded to an aromatic ring, as in the phenolic compound having a group, the photosensitive resin composition according to the first embodiment of the present invention.

Since the properties of the resin film finally obtained depend on the raw material resin used, the ratio (s / t) to the amount of the repeating unit (2) in the repeating unit (1) does not need to be specified in the copolymer structure of the resin component.

However, in the case where the photosensitive resin composition dissolved in the alkaline developer is in a positive form depending on the type of photosensitive agent described later, even if the part exposed to light is in a positive form, the solubility in the alkaline developer and also the result of increasing the unexposed part, polyamide The number of carboxyl groups in the acid increases as the value of t mentioned above increases.

It is impossible to make a sufficiently large difference in solubility in alkaline developing solution between the exposed and non-exposed portions in the developing step.

Alternatively, if the value of t is unduly small, there is a tendency for any part of the diamine 5 to remain unreacted, with the tendency for photosensitizer stability to be reduced.

It is desirable for the s / t value to fall within the 2-20 range.

The arrangement order of the repeating unit (1) and the repeating unit (2) in the copolymer structure of the resin component is not particularly limited to the photosensitive resin composition according to the third embodiment of the present invention.

Alternatively, it is possible that the polyamic acid derivative of the copolymer structure is any of alternating copolymers, random copolymers and block copolymers.

The photosensitive resin composition of this invention contains a photosensitive agent.

In the present invention, the photosensitizer can be generally used in the photosensitive resin composition of the first, second and third embodiments.

Particular compounds used as photosensitizers in the present invention include, for example, o-quinone diazide compounds, azide compounds and diazo compounds.

When using o-quinone diazide compounds, compounds having at least one o-quinone diazide group in the molecule, for example, compounds QD-1 to QD-15 shown in Table A, may be used singly or in combination. Can be.

For example, 1,2-naphquinone diazide sulfonic acid, which is 2,3,4-trihydroxy benzopinone, such as the QD-1 and QD-2 compounds shown in Table A and QD-4 and QD- shown in Table A The use of an aromatic ester which is o-naphthoquinone diazide sulfonic acid, including 1,2-naphthoquinone diazide sulfonic acid ester of 2,3,4,4'-tetrahydroxy benzophenone as a compound 5, as a photosensitizer Particularly preferred.

For example, 1,2-taphthoquinonediazide-5-sulfonic acid ester of compound QD-4 WMR, 2,3,4,4'-tetrahydroxybenzophenone is suitable for use as a photosensitizer for g-ray exposure. Do.

Compound QD-5, i.e., 1,2-naphthoquinonedaazide-4-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone, is exposed to ultraviolet light with a wavelength shorter than the g-ray wavelength Suitable for use as a photosensitizer for.

In the photosensitizer of 1,2-naphthoquinone diazide-4-sulfonic acid ester of 2,3,4,4'-tetrahydroxybenzophenone, 1,2-naphthoquinone diazide-4-sulfonic acid and 2, The esterification rate of 3,4,4'-tetrahydroxybenzophenone is generally from 40 to 100% based on the total number of hydroxyl groups contained in the benzophenone compound.

Alternatively, the number of naphthoquinone diazide groups introduced into a single molecule of 2,3,4,4'-tetrahydroxybenzopanone having four hydroxyl groups is on average 1.6-4. The photosensitizer corresponds to a sulfonic acid mixture with 1,2,3 or 4 naphthoquinone azide compounds.

In the present invention, it is also possible to use 1,2-naphthoquinone diazide-4-sulfonic acid esters, for example, compounds QD-16 to QD-51 in Table B as o-quinone diazide compounds which act as photosensitizers. It is possible.

The naphthoquinone diazide compounds can be readily prepared by reacting naphthoquinone diazide sulfonyl chloride represented by the general formula given below of either alcohol, phenol or amine to remove HCl:

When an azide compound is used as a photosensitive agent contained in the photosensitive resin composition of the present invention, the compounds A-1 to A-28 shown in Table C may be used singly or in combination.

When the diazo compound is used as a photosensitizer in the photosensitive resin composition of the present invention, it is preferable to use the diazo compound represented by the general formula (18) shown below:

Wherein the same or different R ¹⁰ and R ¹¹ are substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted allyl groups, 1 to 20 carbon atoms and silicon A substituted or unsubstituted aryl group having a substituted alkyl group or a silicon atom). The diazo compound represented by formula (18) above forms a fine polyamide film pattern especially when deep ultraviolet rays are used. do.

Certain compounds DA-1 to DA-22 shown in Table D may be used singly or in combination as diazo compounds represented by formula (18).

The photosensitive resin compositions according to the first to third embodiments of the present invention can be prepared as follows by using the above-described resin component and photosensitive agent.

In particular, the photosensitizer is dissolved in a resin component solution synthesized in an organic solvent as previously described for preparing the glaze. It is preferable that the glaze has a polymer (resin component) concentration of 5 to 40% by weight.

At the time of manufacture of the glaze, the amount of the photosensitizer must be adjusted as follows.

In the case of the photosensitive resin composition according to the first or third embodiment of the present invention, a polyamic acid derivative or repeating unit (1) having a repeating unit represented by (1) or a repeating unit (2) It is preferable to fix the photosensitive agent amount with the polyamic acid of a copolymer structure, 0.1-30 weight part of 100 weight part bases of a quantity.

When the amount of the photosensitizer is smaller than 0.1 part by weight, the resulting photosensitive resin composition does not exhibit a sufficiently high sensitivity to light in the exposing step.

Otherwise, when the amount of the photosensitizer is greater than 30 parts by weight, it is impossible to achieve a sufficient difference in solubility in the developer between the exposed and unexposed portions of the photosensitive resin composition layer while failing to obtain the desired polyimide film pattern.

In the case of using the photosensitive resin composition according to the second embodiment of the present invention, a polyamic acid derivative having a repeating unit (1) fixed at a high 100 parts by weight, a polyamic acid having a repeating unit (2), and a photosensitive agent It is preferred to fix the amount with a photosensitizer so as to fall within the range of 5-50 parts by weight, preferably 10-50 parts by weight.

If the amount of the photosensitizer is smaller than 5 parts by weight, the resulting photosensitive resin composition does not exhibit sufficiently high sensitivity to light in the light exposure step.

Alternatively, if the amount is greater than 50 parts by weight, residues of the photosensitive component after development cause serious problems.

As a preferable photosensitive agent, it is possible to add dyes, surfactants, alkali-dissolving resins and the like to the photosensitive resin composition of the present invention.

Alkali-soluble resins that are not particularly limited in the present invention include, for example, poly-p-vinylphenol, poly-o-vinyl phenol, poly-m-isopropylphenol, m, p-crogel novolak resin xylene sol novo Lac resins, copolymers of p-vinyl phenol and methyl methacrylate, copolymers of p-isopropenyl phenol and male anhydride, polymethacrylic acid and polymers with repeating units shown in Table E.

The action of the photosensitive resin component according to the first to third embodiments of the present invention is described with respect to a method of forming a polyimide deactivated film or a polyimide interlayer insulating film using the composition.

The photosensitive resin composition of the present invention has different functions in the exposure and development steps depending on the chemical structure of the resin component used, the type of photosensitive agent used, and the pattern formation method.

The following description relates to the case where o-quinone diazide compounds and azide compounds are used as photosensitizers.

The operation of the photosensitive resin composition of the present invention will first be described when an o-quinone diazide compound, i.e., 1,2-naphthoquinone diazide-5-sulfonic acid ester, is used as the photosensitizer.

In this case, the photosensitive resin composition according to the first to third embodiments of the present invention functions substantially the same.

In a first step, the photosensitive resin composition according to any one of the first to third embodiments of the present invention containing 1,2-naphthoquinonediazide-5-sulfonic acid ester as a photosensitizer is filtered to remove fine impurities from the composition and The semiconductor support is then coated with the composition by spin coating or deposition.

The coating is then heated and dried (baked) to form the photosensitive resin composition layer.

It should be noted that the photosensitive resin composition of the present invention exhibits good solubility in a solvent.

This facilitates the coating method and as a result the composition is suitable for forming a thick layer.

In the next step, the photosensitive resin composition layer is first cured at 60-100 ° C. and then exposes the composition layer through a mask pattern desired for energy beams such as X-ray visible light, infrared light, ultraviolet light and electron beam (exposure step).

In this step, the portion 19 of the o-naphthoquinone diazide sulfonic acid ester of the photosensitizer in the exposed portion of the photosensitive resin composition is represented by the general formula (20) shown below for the photochemical reaction with water in the system, as shown below. Converted to expressed ketones:

Where R 'represents a monovalent organic group.

After the light exposure step, a firing treatment is applied on the photosensitive resin composition layer at about 90 to 200 ° C. for about 5 seconds to 60 minutes.

By this baking treatment, the ketone 20 formed as the result of the exposure reacts with the active hydrogen contained in the resin component at the exposed portion so as to crosslink the polymer chain.

Alternatively, o-naphthoquinone diazide sulfonic acid ester contained in the resin composition is partially degraded by calcining in a non-irradiated portion (non-exposed portion).

In the next step, the photosensitive resin composition layer is developed after firing by, for example, a deposition method using an aqueous alkali solution or a spraying method (development step).

The aqueous alkali solution used in the present invention is an aqueous inorganic alkali solution such as potassium hydroxide or sodium hydroxide aqueous solution and organic alkali aqueous solution such as propyl amine, butyl amine, monoethanol amine ethylene diamine, trimethylene diamine, trimethyl ammonium hydroxide, hydrazine or tetramethyl ammonium hydroxide Aqueous solution.

The aqueous alkali solution may be used singly or in combination.

It is also possible to add inexpensive solvents for the photosensitive resin composition of the invention such as methanol, ethanol, 2-propanol, ethylene glycol, ethylene cellosolve, butyl cellosolve diethylene glycol ethylcarbitol or water to the amine compound. .

Alternatively, the above-mentioned amine compound may be used to prepare the photosensitive resin composition of the present invention such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetoamide, or dimethyl sulfoxide. It can be mixed with the solvent used to.

With the result that the ability to inhibit degradation in the alkaline solution inherent in the photosensitive composition decreases or disappears, the photosensitizer, o-naphthoquinone diazide sulfonic acid ester, is partially degraded in the unexposed portion of the photosensitive resin composition layer.

Thereafter, the non-exposed portion can be dissolved in the alkaline developer.

In the exposed portion, however, the resin component is crosslinked as previously described.

As a result of increased molecular weight of the resin component, the resin component does not dissolve in the alkaline developer.

Alternatively, the exposed portion itself remains not selectively removed in the development stage.

As described above, the photosensitive resin composition according to any one of the first to third embodiments of the present invention uses a negative photosensitive material, i.e. in some cases a pattern using o-naphthoquinone diazide-5-sulfonic acid ester as the photosensitizer. When formed by the above-described steps, the exposed and developed steps perform the action of the photosensitive material in which the exposed portion becomes insoluble in the current solution. However, the above-mentioned action is not necessarily made in the method of forming the pattern.

It should also be mentioned that in the case of using o-quinonediazide compounds as the photosensitizer, it is possible to omit the post-exposure firing, ie post-exposure firing (PEB) firing.

In the above-described method of forming the pattern, such post-exposure plasticity has already been partially integrated into the photosensitive resin composition layer in order to control the dissolution rate of the composition layer in the alkaline developing solution and to improve the contrast of the finally obtained pattern. It is very effective in partially imidizing for dehydration.

In addition, the post-exposure firing improves the bonding between the resin composition layer and the semiconductor support, with the result that the resin composition layer can prevent the semiconducting support from being peeled off in the developing step.

Furthermore, post-exposure firing contains polyamic acid derivatives as resin components which are introduced into the side chains of the derivatives having hydroxyl groups bound in aromatic rings and which do not have substituent groups which are o-naphthoquinone diazide compounds as photoreceptor components. Even in the case of using one photosensitive resin composition, satisfactory negative patterns are formed.

More specifically, the above-mentioned polyamic acid derivatives include alcohol compounds, amine compounds, alkoxides as compounds for introducing substituent groups into the polymer side chain in the synthesis of the polyamic acid derivatives described above, each of which is incorporated into the aromatic ring. Phenolic compounds having no hydroxyl group bound or having only one hydroxyl group bonded to an aromatic ring.

Repeatedly, when the photosensitive resin composition contains the above-mentioned special polyamide acid derivative, the post-exposure property makes it possible to form a satisfactory negative pattern.

Satisfactory negative pattern formation is derived from the reaction described below.

In particular, post-exposure firing causes the o-naphthoquinone diazide sulfonic acid ester contained in the water composition to partially degrade to form ketene in the non-exposed portion of the vertical composition layer.

The resulting ketene is converted to carboxylic acid by water in the system while increasing the solubility of the non-exposed portion in the alkaline developing solution.

Since the substituent group having no hydroxyl group bonded to the aromatic ring is introduced into the side chain, the non-exposed portion may be dissolved in the alkaline developer even in the case of using a polyamide acid derivative having low solubility in the alkali developer. Can be.

Alternatively, post-exposure firing may be performed by using a polyamide acid derivative having a substituent group having hydroxyl groups bonded to an aromatic ring and introduced into the side chain, while preventing the exposed portion from substantially dissolving in the alkaline developing solution. It is possible to crosslink the resin component in the exposed portion.

In conclusion, only the exposed portion is left unremoved in the development stage to selectively form a satisfactory voice pattern.

In addition, when the photosensitive resin composition according to any one of the first to third embodiments of the present invention contains an o-quinone azide as a photosensitizer, the composition may be subjected to various treatments in addition to the pattern step including the post-exposure firing described above. Thereby allowing the action of the negative photosensitive material.

Moreover, negative photosensitivity exposes the entire support coated with the base composition after exposure to ultraviolet light and post-exposure bake step, for example by adding a base material such as imidazole to the resin composition to the photosensitive resin composition of the present invention. Or by heating the support after an exposure step of ammonia alkylamine, such as ammonia, alkyl amine, etc., under a steam atmosphere.

Furthermore, in order to remove residues in the development, it is possible to rinse with water, alcohol, acetone, and the like after the development and then apply a calcination treatment.

In the photosensitive resin composition of the present invention using the o-quinone diazide compound as the photosensitizer, it is particularly preferable to form a pattern according to the method described above.

In this case, post-exposure firing is not required even if the photosensitive resin composition performs a different action from that described above in this case.

In particular, the o-naphthoquinone diazide sulfonic acid ester portion 19 of the molecule in the exposed portion of the photosensitive resin composition layer of the present invention is photoexposed by optical reaction and by water present in the system, as previously described. Then converted to ketene 20.

Then, the development after the exposure step is applied to the photosensitive resin composition layer without firing.

The development is carried out by a deposition method or spraying method using an aqueous alkali solution.

In the non-exposed part of the photosensitive resin composition layer, it should be mentioned that o-naphthoquinone diazide sulfonic acid ester is applied as a decomposition inhibitor which prevents the resin composition from dissolving in aqueous alkali solution.

The non-exposed portions of the resin composition layer are made to be less soluble in the developer than the polymer itself.

In the exposed portion of the photosensitive resin composition layer, however, ketene 20 converted by photochemical reaction from o-naphthoquinone diazide sulfonic acid ester as described above is also removed by water present in the system as shown below. Converted to carboxylic acid 21:

Where R 'represents a monovalent organic group. Since the carboxyl groups of the carboxylic acid 21 react with alkali metal ions or ammonium ions present in the alkaline region to form salts, the resultant portions can be dissolved.

In other words, the non-exposed part itself is left unremoved in the developing step.

As described above, if the composition contains an o-quinonediazide compound, i.e. 1,2-naphthoquinone diazide-5-sulfonic acid ester as a photosensitizer, the development is applied without adopting post-exposure properties. , The photosensitive resin composition according to any one of the first to third embodiments of the present invention functions as a positive photosensitive material that allows the exposed portion to be dissolved in the developing solution.

In the case where the composition performs the function of the positive photosensitive material, however, the carboxylic acid 21 formed in the exposed portion does not allow the exposed portion in the developer to sufficiently dissolve in some cases.

In such a case, the carboxyl group having the repeating unit represented by the general formula (2) is contained in the resin component, and the carboxyl mentioned above, as long as the photosensitive resin composition according to any one of the second and third embodiments of the present invention becomes It acts similar to that performed by the carboxyl group of acid (21).

Since the carboxyl group of the repeating unit (2) also forms an alkali salt, the solubility of the exposed portion of the photosensitive resin composition in the alkaline developer is encouraged to improve the decomposition of the finally formed polyamide film pattern.

As previously described, it is possible to rinse with water, alcohol, acetone and the like after the development and to carry out calcining to remove the developer residue.

As previously described, it is possible for the photosensitive resin composition according to any one of the first to third embodiments of the present invention to contain an azide compound as a photosensitizer.

It is possible to contain an azide compound as a photosensitizer.

In the case of containing an azide compound as the photosensitizer, the photosensitive resin composition according to the first to second embodiments of the present invention performs substantially the same function.

In the first step, as in the case of applying a support having a composition containing an o-quinone diazide compound, the semiconductor support is applied with a photosensitive resin composition containing an azide compound as a photosensitive agent.

The photosensitive resin composition layer is cured in advance, and then the surface of the resin composition layer is irradiated with such an energy beam as described previously in a preferred mask pattern.

In this step, the azide compound 22 shown below contained in the irradiated portion (exposed portion) of the photosensitive resin composition layer is converted into nitrate radicals 23 by light irradiation as shown below:

The resulting nitrate radicals 23 react with hydroxyl groups bonded to aromatic rings introduced into the polyamic acid derivatives in the resin component of the exposed portion, and double bonds of the resin component to crosslink the polymer chains of the resin component. Hydrogen-recovery reaction and crosslinking reaction.

In the next step, firing, ie post-exposure firing, is applied to the photosensitive resin composition layer after the exposure step at about 90 to 200 ° C. for about 5 seconds to 60 minutes.

Post-exposure firing also enhances the crosslinking of the polymer chains of the resin component in the exposed portion, ie the crosslinks formed by the action of the nitrate radicals 23 in the exposed portion.

After post-exposure firing, development is applied to the photosensitive resin composition layer by deposition method spraying methods using an aqueous alkali solution as in the previously described development.

In the non-exposed portion of the photosensitive resin composition layer, the hydroxyl group bonded to the aromatic ring remaining in the polyamic acid derivative in the resin component reacts with the alkali metal ion or ammonium ion remaining in the alkaline developer to form phenoxide. As a result, the resin composition is dissolved in the alkaline developer.

In the exposed portion, however, the resin component is crosslinked as described above, so that the molecular weight of the resin component is increased and the resin composition is not dissolved in the alkaline developer.

Thereafter, it is not selectively removed without being removed after developing the exposed part.

In other words, the photosensitive resin composition according to any one of the first to third embodiments of the present invention acts as a negative photosensitive material, wherein the composition contains an azide compound as a photosensitive agent and the pattern formation is performed by the method described above. The exposed portion becomes insoluble in the developing solution at the exposure and development stages.

In the case of using the azide compound as the photosensitizer, it is possible to omit post-nozzle firing as in the case of using the previously described o-quinone diazide compound. However, it is desirable to apply post-exposure firing in order to control the formed pattern and to improve the bonding between the resin composition film and the semiconductor support.

In addition, it is possible to apply a rinsing treatment with water, alcohol, acetone and the like after the development in order to remove the developer residue, and to apply a calcination treatment.

In the present invention, by using the photosensitive resin composition of the present invention, it is possible to form a thin polyamic acid film on a support before forming an inactive film or an interlayer insulating film.

In this case, the semiconductor support is first applied with polyamide acid and then about 90-200 ° C. for about 10 seconds to 60 minutes to form a polyamide acid film having a thickness of about 0.1 to 100 microns, preferably about 0.2 to 50 microns. The coating is heated and dried (baked).

The polyamic acid film is then also applied with the photosensitive resin composition of the present invention to a thickness of about 0.5 to 100 microns and then heated the resin composition coating to 70 to 170 ° C. for about 10 seconds to 60 minutes to form a resin composition layer. And dry (fire).

After forming the resin composition layer, a pattern formation method such as light-exposure and development described above is applied.

The polyamic acid film first formed on the support is not particularly limited as long as the polyamic acid exhibits satisfactory heat resistance and high bonding strength with the support.

Generally, polyamic acids prepared by the reaction between acid anhydrides and diamines are used.

In order to improve the bonding on the polyamic acid membrane and the support, it is possible to use polyamic acid copolymers having small amounts of siloxane diamine units.

It is also possible to add small amounts of silane coupling agent to the polyamic acid.

In addition, in order to add plasticity to the main chain of the polyamic acid and to improve the bonding between the polyamic acid film and the support, it is possible to use a polyamic acid having a benzopinone skeleton or a biphenyl skeleton in the acid component.

It is generally mentioned that polyamic acid membranes do not achieve high conjugation with the support if the polyamic acid molecular weight is unduly small.

As a result, the polyamic acid used to form the film on the support preferably has at least 10,000 molecular weight.

In the case where the polyamic acid film is previously formed on the support surface as described above, it is possible to improve the bonding between the resin composition and the support.

Even in this case, the photosensitive resin composition of the present invention performs the action of the positive or negative photosensitive material in the light exposure and developing step depending on the chemical structure of the resin component, the type of photosensitive agent used and the pattern formation method adopted.

Incidentally, the polyamic acid film first formed on the support is simultaneously developed with the photosensitive resin composition layer of the present invention in the developing step.

The above-described line treatment to form a polyamic acid film on a support is also carried out in the case of using a polyimide membrane pattern using alkali-soluble photosensitive polyimide described in Japanese Patent Application Laid-Open No. 89-630 mentioned above. It is also effective.

In this case, a polyamic acid thin film is first formed on the semiconductor support and then a photosensitive polyimide film is formed on the polyamic acid film.

In addition, exposure and development are preferably applied to the photosensitive polyimide film to form a desired pattern.

It is mentioned that the polyamic acid film first formed on the support is developed by the developing step by alkali development simultaneously with the photosensitive polyimide film.

In the next step, the resulting pattern is heated to cure and obtain the desired polyimide film pattern.

It is important to mention that the above-mentioned pre-treatment improves the bonding between the polyimide film pattern and the semiconductor support.

Table F shows examples of the photosensitive resin composition of the present invention which is preferably used in the method for forming a polyimide film pattern composed of a step of forming a polyamic acid film on the support surface in advance.

Regardless of the type of photosensitive agent used and the method of forming the adopted polyimide film pattern, the photosensitive resin composition according to any one of the first to third embodiments of the present invention performs the functions described below.

After development, the photosensitive resin composition layer of the predetermined pattern is heated at the predetermined temperature.

The heating removes the substituent introduced into the side chain of the polyamic acid derivative having the repeating unit (1), the azide compound for crosslinking the polymer chain of the resin component, the o-quinone diazide compound contained in the resin component, and the like.

In addition, heating evaporates the solvent components remaining in the applied film.

As a result, the polyamic acid is cyclized to form a polyimide film pattern having repeating units represented by the general formula (24) given below.

In the heating method, it is desirable to gradually increase the temperature from room temperature to a final eg temperature of 150 to 45 ° C.

If the final heating temperature is lower than 150 ° C., the polyamic acid derivative is not imidized in the polyimide formation step.

If the polyamic acid derivative remains partially unreacted, the thermal stability of the polyimide film formed is reduced.

Alternatively, if the final heating temperature is above 450 ° C., the imidized polymer tends to decompose, resulting in reduced thermal stability.

A semiconductor device enclosed in a resin capsule uses an encapsulating resin such as an epoxy resin in a semiconductor support having a polyimide film pattern formed on its surface, for example, by using the photosensitive resin composition according to any one of the first to third embodiments of the present invention. It is prepared by applying a general encapsulation method.

Since the patterned polyimide film exhibits excellent electrical insulation, high pipe resistance and excellent heat resistance, the patterned polyimide film serves as a satisfactory inert film or interlayer insulating film in semiconductor devices.

As described above, the photosensitive resin composition according to any one of the first to third embodiments of the present invention may be subjected to two different functions, namely, the action of positive or negative photosensitive materials in the photo-exposure and development steps and the inert film used in the semiconductor device or The function of the polyimide film used as the interlayer insulating film is performed.

The use of the photosensitive resin composition of the present invention makes it possible to continuously perform the resist method and the polyimide film forming method to form a pattern on the polyimide film which is alternately performed by two different methods for patterning the inert film or the interlayer insulating film. Let's do it.

Since it is possible to form a polyimide film pattern without using the resist separately, the composition of the present invention simplifies the method of forming the polyimide film pattern.

The photosensitive resin composition of the present invention can also be used as a photoresist for general microfabrication for PEP.

In this case, the photosensitive resin composition layer is formed on the support by a previously described method, and then optionally by a dry etching or wet etching method, optionally with a patterned resin composition layer used as an inner etching mask. Etch

By post-exposure baking, i.e., by using post-exposure baking which is preferably employed in the method of forming an inert film or an interlayer insulating film using the photosensitive resin composition according to any one of the first to third embodiments of the present invention described above. It is also possible to form a pattern by using known precursors of polyimides other than the photosensitive resin composition of this invention.

In this case, the photosensitive resin composition according to the fourth embodiment of the present invention is prepared by mixing the resin component of the polyamic acid having the repeating unit (2) given above and the photosensitizer of the naphthoquinone diazide compound.

More specifically, the resin layer containing the resin composition of the fourth embodiment as a main component is formed on the support, optionally exposing the resin layer to light and subsequently applying a calcination treatment to the resin layer at 130 to 200 ° C.

Further, after the development is applied to the resin layer after the firing treatment, the polyamic acid having the repeating unit (2) is imidated, and as a result, the developed resin layer is heated after the development to form a polyimide film pattern.

In the photosensitive resin composition of the fourth embodiment, a compound similar to the polyimide acid contained in the resin component of the composition according to the second embodiment of the present invention can be used as a polyamic acid having a repeating unit (23).

Alternatively, the naphthoquinone diazide compound used as the photosensitizer in the composition of the fourth embodiment is not particularly limited.

In a fourth embodiment, it is possible to use those similar to the compounds used in the composition of any one of the first to third embodiments of the invention.

For example, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, 2,1-naphthoquinone diazide-4-sulfonic acid as a photosensitizer It is possible to use 2,1-naphthoquinone diazide-5-sulfonic acid and its derivatives such as salts, esters and amides.

Particular preference is given to using 1,2-naphthoquinone diazide-5-sulfonic acid esters.

It is also preferable to use the compounds QD-16 to QD-51 shown in Table B previously referenced in connection with the photosensitive resin composition according to the first to third embodiments of the present invention.

In the photosensitive resin composition according to the fourth embodiment of the present invention, naphtho is contained in an amount of 5 to 70 parts by weight, preferably 25 to 45 parts by weight, based on 100 parts by weight of polyimide acid having a repeating unit represented by formula (2). Preference is given to using quinone diazide compounds.

If the naphthoquinone diazide compound is used in an excessively large amount, the thickness of the resin layer is unduly reduced by heating in the imidization step, and the decomposition of the resulting polyamide film pattern tends to be reduced.

In the photosensitive resin composition of the fourth embodiment, the compound is used in an organic solvent such as methylethyl ketone, giclohexane, acetate cellosolve, N, N-dimethylformamide N-methyl-2-pyrrolidone or hexamethyl phospho triamide. It is possible to add the naphthoquinone diazide compound in the form of a solution prepared by dissolving it.

In the method for forming the polyimide film pattern described above, the positive or negative pattern is selected by appropriately selecting the type, post-exposure conditions, etc., of the naphthoquinone diazide compound contained as a photosensitive agent in the photosensitive resin composition of the fourth embodiment. It is possible to form.

The reason for the specific action is not yet clear enough. For example, in the case of using 1,2-natroquinone diazide-4-sulfonic acid ester as the photosensitizer, it is believed that the chemical reaction takes place as described below.

In particular, the above-mentioned photosensitizers are considered to undergo the reactions shown below in the exposed and non-exposed portions of the resin layer during the exposure and development steps.

In the exposed portion of the photosensitive resin composition of the third embodiment, the 1,2-naphthoquinone diazide-4-sulfonic acid ester 25 is converted to indene carboxylic acid in the exposure step and at the same time given the reaction formula (a) As shown in 1-sulfo-3-carboxylidene 26 and the backbone moiety, ie the main chain portion of the polyamic acid:

Here, R 'represents a monovalent organic group.

Furthermore, the reactions (b) to (d) given below take place in the post-exposure firing, ie in the exposed part in the post-exposure firing step:

(b) 1-Sulfone-3-carboxylidene formed in the exposure step partially imidates the polyamic acid with repeating unit (2).

(c) Indene carboxylic acid is decarboxylated to be converted to indene derivatives.

(d) When the 1,2-naphthoquinone diazide-4-sulfonic acid ester used is multifunctional, the unreacted 1,2-naphthoquinone diazide-4-sulfonic acid ester is crosslinked in the light exposure step. do. Alternatively, the reactions (e) and (f) given below occur in the post-exposure firing step in the non-exposed portion of the photosensitive resin composition of the fourth embodiment:

(e) 1,2-naphthoquinone diazide-4-sulfonic ester is decomposed to convert to indene carboxylic acid.

(f) When the 1,2-naphthoquinone diazide-4-sulfonic acid ester used is multifunctional, the unreacted 1,2-naphthoquinone diazide-4-sulfonic acid ester is subjected to the photo-exposure step. Crosslinked. Regarding the exposed portion of the photosensitive resin composition in the fourth embodiment, the solubility in the alkaline developer is enhanced by the reaction (a) given above. In contrast, the solubility in alkaline developer is lowered by reactions (b) to (d). Alternatively, the solubility of the non-exposed portion in the alkaline developer is increased by reaction (e).

In contrast, the solubility in alkaline developer is lowered by reaction (f). In the method of forming the polyimide film pattern described above, when the contribution of reaction (a) is greater than that of reactions (b) to (d), a positive pattern is finally formed and reactions (b) to (d) It is considered reasonable to understand that the negative pattern is finally formed when the contribution of is greater than in the case of reaction (a).

In the exposed portion of the photosensitive resin composition of the fourth embodiment, any of the reactions (a) or (b) to (d) which are more dominant are the type of naphthoquinone diazide compound used as the photosensitizer, the photo-exposure condition, the exposure step It depends on the firing conditions.

In the method for forming the polyimide film pattern described above, it is possible to form a positive or negative pattern by selecting various conditions suitably.

When using the photosensitive resin composition according to the fourth embodiment of the present invention, it is possible to form a polyimide film pattern by substantially the same method as when using the composition according to any one of the first to third embodiments of the present invention. Do.

In particular, the polyamic acid and the naphthoquinone diazide compound having the repeating unit (2) are dissolved in a suitable organic solvent and fine impurities are removed from the solution, for example, by filtration in order to prepare the photosensitive resin composition in glazing.

Then, a support such as a semiconductor support is applied with the glaze by, for example, an s rotation coating method or a deposition method, and then the coating is heated and dried (baked) to form a resin layer.

In the next step, the surface of the resin layer is selectively exposed through a mask pattern desirable for an energy beam such as X-rays, visible light, infrared rays, ultraviolet rays or electron beams (exposure step).

It is possible to adopt either contact or injection exposure system.

After the exposure step, the resin layer is calcined at 130 to 200 ° C., for example, hot plated, to cool the resin layer.

If the temperature for the firing treatment is unduly low, the resulting pattern does not exhibit sufficiently high decomposition.

Otherwise, if the temperature for the firing treatment is unduly high, the solubility of the resin layer in the alkaline developer becomes low and it becomes difficult to carry out subsequent development.

The calcining treatment should preferably be carried out at a temperature which falls within the range of 140 to 160 ° C.

The firing time dependent on the firing temperature should generally be from 0.5 to 60 minutes, preferably from about 1 to 4 minutes.

If the firing time is unreasonably short, the resulting pattern does not exhibit sufficiently high decomposition.

Otherwise, if the firing treatment time is unreasonably long, the subsequent phenomenon applied to the resin layer becomes difficult.

After the firing treatment, development is applied to the resin layer using the alkaline aqueous solution.

In this step, the exposed or unexposed portions of the resin layer are optionally dissolved in the developer and are subsequently removed to form the desired positive or negative pattern.

As aqueous alkali solution, it is possible to use an organic or inorganic alkaline solution used for developing the resin layer of the photosensitive resin composition according to any one of the first to third embodiments of the present invention.

Moreover, the resin layer having the pre-determined pattern developed as described above is heated at the pre-determined temperature.

As a result, the polyamic acid having the repeating unit 2 contained in the resin layer is cycled (imidized) to form a polyimide film pattern having the repeating unit represented by the general set 27 given below.

In the heating process, it is desirable to raise the temperature, tangently from room temperature to the final heating temperature of 90-400 ° C.

If the temperature rises rapidly during heating, the polyamic acid does not partially imidize during the polyimide formation.

If polyamic acid remains partially unreacted, thermal stability tends to decrease.

The semiconductor device encapsulated with a resin capsule applies a general encapsulated method using a resin encapsulated such as an epoxy resin to a semiconductor support having a polyimide film pattern formed on a surface by a special method according to the fourth embodiment of the present invention. It can be prepared by.

Since the patterned polyimide film exhibits excellent electrical insulation, high light resistance and good heat resistance, the patterned film can suitably be used as an inactive film or an interlayer insulating film in a semiconductor device.

Like the photosensitive resin composition according to any one of the first to third embodiments of the present invention, the fourth embodiment composition employs a suitable method to induce two different actions, namely the action of the positive or negative photosensitive material and the inert film in the photo-exposure and development steps. Alternatively, the polyimide film serving as the interlayer insulating film can be performed.

The method for forming the polyimide film pattern using the photosensitive resin composition of the fourth embodiment can continuously carry out the resist method for patterning the polyimide film and the method for forming the polyimide film, which alternatively employs two different methods. Is performed.

Since it is possible to form a polyimide film pattern without using a resist separately, the composition of this invention makes the composition of the method of forming a polyimide film pattern the method of forming a polyimide film pattern.

Furthermore, the polyimide film pattern formed by a special method using the photosensitive resin composition according to the fourth embodiment of the present invention can be used in general dry etching or wet etching methods as an anti-etching mask for general fine etching treatment for PEP. .

The technical scope of the present invention is not limited by the following embodiments without needing to describe and re-embodiment embodiments of the present invention in order to more clearly present the technical idea of the present invention.

Examples 1 to 29, given below, relate to the photosensitive resin compositions according to the first to third embodiments of the present invention, and the chemical structures of the compounds referred to in the above examples abbreviation and Tables 1-11 contained in the examples are given in Table G. It is.

Example 1

Four different flasks with 100 ml internal volume spread as nitrogen gas 2.1 / 8 g (0.01 mol) pyromellitic dianhydride (PMDA), 2.48 g (0.02 mol) 3-hydroxybenzyl alcohol, and 10 ml Filled with N-methyl-2-pyrrolidone (NMP).

The mixture is stirred at room temperature for 24 hours to obtain dihydroxy benzyl pyrrolidate.

The temperature in the flask was then lowered to 0 ° C. and a solution prepared by dissolving 2.00 g (0.1 mol) of 4,4′-diaminodiphenyl-ether (ODA) in 10 ml of NMP while stirring the system. Add.

Furthermore, it was dripped in the flask for 25 minutes of the solution prepared by dissolving 4,53 g (0.02 mol) of dicyclohexyl carboimide (DCC) in NMP. Thus, the reaction solution is maintained at 5 ° C. for 4 hours while the reaction is carried out, and the precipitate formed by filtration under reduced pressure is removed.

The resulting filtrate is quenched in 60 ml water to obtain a polyamic acid ester precipitate.

1,2-naphthoquinone diazide- of 0.46 g 2,3,4,4'-tetrahydroxy benzophenone (ester substitution number of 3) dissolved in 2.0 g polyamic acid ester 8 g NMP and acting as a photosensitizer Sulfonic acid esters are added to the solution.

The solution is then passed through a filter having a processing size of 0.5 microns to obtain the photosensitive resin composition according to the first specific embodiment of the present invention.

Example 2-4

The photosensitive resin composition according to the first specific example of the present invention was prepared by the same method as Example 1 using the raw material composition shown in Table 1 described below.

Example 5

2.0 g of the polyamic acid ester prepared in Example 1 was dissolved in 8 g NMP, 0.40 g 2, as a photosensitizer in the solution to prepare a photosensitive resin composition according to the first specific embodiment of the present invention (see Table 1) 6-di- (4'-azidebenzal) -4-methyl cyclo-hexanone is added.

Each photosensitive resin composition of the first example prepared in Example 1-5 is subjected to a measurement test with respect to various properties as follows.

[Test 1]: (resolution measurement)

A silicon wafer was applied with the photosensitive resin composition by a rotation coating method using a spinner.

The coating is then heated and dried at 90 ° C. for 5 minutes, exposing the dry film to dianhydride light for 60 seconds through a circular mask.

Exposure equipment (PLA-500F manufactured by Canon Inc.) was used in the exposure process. After exposure the silicon wafer was deposited in alkaline developer (ie, 2.38 wt% aqueous tetramethyl ammonium hydroxide (TMAH) solution) for 90 seconds to develop and washed with water to form the desired prototype.

Using the photosensitive resin composition prepared in Example 1-5, each formed circular cross section was observed on an electron microscope (SEM). Table 2 shows the test conditions and results.

[Test 1 ']: (Resolution Measurement)

A silicon wafer having a 3 inch diameter was applied by the photosensitive resin composition prepared in Example 1.

The coating was heated and dried for 10 minutes in a hot place at 90 ° C. to obtain a dry film with a thickness of 5 microns.

Thereafter, the film was exposed to ultraviolet light through a circular mask using the above-described exposure apparatus PLA-500F.

After exposure, the silicon wafer was calcined for 10 minutes on a 150 ° C. hotplate, and the silicon wafer was immersed for 90 seconds in an alkaline developer (2.38 wt% aqueous solution of TMAH) to develop.

Finally the wafer was washed in water to form the desired prototype.

Thus, the circular cross section formed was observed with an electron microscope (SEM).

In Table 2 the test conditions and results of test 1 'are shown.

The results shown in Table 2 show that the polyimide film pattern formed using the photosensitive resin composition according to the first specific embodiment of the present invention exhibited the preferred resolution using a polyimide film pattern such as a protective film or an interlayer insulating film in a semiconductor device. lost.

In addition, tests 1 and 1 'show that the pattern on which the post-exposure baking treatment (i.e. post-exposure baking) is formed is effective for improving the resolution.

TABLE 1

b ^* : compound reacted with a ^*

The description in the specification should be referred to in the context of compound abbreviations.

TABLE 2

a ^* : firing distance between exposure and development (corresponds to test 1 ')

d ^* : Developer, TMAH aqueous solution (% by weight)

e ^* : P… Positive pattern, N. Voice pattern

Example 6

Four branched flasks with 500 ml internal volume purged with nitrogen gas were filled with 10.91 g (0.05 mol) PMDA and 60 ml NMP and cooled to 0 ° C.

Then, a solution prepared by dissolving 10.01 g (0.05 mol) OPA in 40 ml NMP is slowly poured into the flask.

The reaction solution is stirred for 5 hours while maintaining the reaction solution at 0-5 ° C. to obtain a polyamic acid solution.

In addition, a solution prepared by dissolving 10.91 g (0.1 mol) 4-aminophenol in 100 ml NMP in a polyamic acid solution and another solution prepared by dissolving 20.63 g (0.1 mol) DCC in 40 mm NMP were added.

The resulting reaction solution was stirred at room temperature for 4 hours.

Thereafter, 100 ml ethanol was added to the reaction solution.

The resulting solution was stirred for 2 hours and the insoluble components were removed by filtration.

The filtrate is dropped in 3 liters of methanol to precipitate the polymer.

The precipitated polymer was separated by filtration and then dried to obtain a polyamic acid derivative.

10 g NMP for 2 g polyamic acid derivative and 0.5 g 1,2-naphthoquinone diazide-4-sulfonic acid ester (3 ester substitutions) of 2,3,4,4'-tetrahydroxy benzophenone Dissolved in and filtered by a filter having a 0.5 micron pore size to obtain a photosensitive resin composition according to the first specific embodiment of the present invention.

Example 7

The 2 g polyamic acid derivative prepared in Example 6 and 0.2 g 2,6-di- (4 'azidebenzal) -4-methylcyclohexane, which acted as a photosensitizer, were dissolved in 10 g NMP, the first specific embodiment of the present invention. Filtration was carried out by a filter having a pore size of 0.5 microns to obtain the photosensitive resin composition according to the example.

[Test 2] (resolution measurement)

Silicon wafers with a 3-inch diameter were applied by the photosensitive resin compositions prepared in Examples 6 and 7, respectively, by a spin coating method using a spinner.

The coating was then heated and dried for 5 minutes on a 100 ° C. hotplate.

The dry film was exposed to light through the pattern mask using the above-described PLA-500F as an exposure apparatus.

After exposure, the silicon wafer was immersed in an alkaline developer (2.38 wt% aqueous solution of TMAH) for 120 seconds to develop and washed in water to obtain the desired pattern.

Therefore, the cross section of each pattern formed using the photosensitive resin composition prepared in Examples 6 and 7 was observed by electron microscope.

A pattern with 20 micron resolution by 350 mJ / cm ² exposure was recognized with respect to the photosensitive resin composition prepared in Example 6.

Furthermore, a pattern with 50 micron resolution by 400 mJ / cm ² exposure was recognized with respect to the photosensitive resin composition prepared in Example 7.

TEST 3: (Phosphosilicate Glass Film and Adhesion Measurement)

Silicon wafers covered with a phosphosilicate glass film (PSG film) were applied to the photosensitive resin compositions prepared in Examples 6 and 7, respectively, by a spin coating method.

Then, the silicon chip having a 2 mm square PSG film formed on the surface was applied to the layer film coated so that the PSG film of the silicon chip could directly contact the coated layer to form a laminated structure composed of the PSG film on the photosensitive resin composition layer on the PSG film. Attach.

The laminated tissue was dried at 90 ° C. for 30 minutes, and 150 ° C. for 30 minutes, 250 ° C. for 1 hour, and 350 ° C. for 30 minutes to form a polymer film having a thickness of about 5 microns controlled between the silicon wafer and the silicon chip. The firing process is performed at.

The resulting sample was maintained for 100 hours in a pressure cooker under steam at 120 ° C. and 2.2 atmospheres.

The shear failure strength of a 2mm square silicon chip attached to a silicon wafer was measured for each pressure cooked (PCT) sample and a controlled sample without PCT.

Shear breaking strength of Example 6 from samples formed by using the photosensitive resin composition in about 100 hours, and the PCT 1.8kg / mm ² (not the PCT) 0 sigan in PCT it was found that with a 2.2kg / mm ^2.

On the other hand, the shear failure strength was found to be 1.6 kg / mm ² at about 100 hours PCT and 2.1 kg / ² at 0 hours PCT in the sample formed using the photosensitive resin composition of Example 7.

Example 8

Four branched flasks with 50 ml internal volume purged with nitrogen gas were filled with 21.8 g (0.1 mol) PMDA, 24.8 g (0.2 mol) 3-hydroxybenzyl alcohol, and 100 ml NMP.

The mixture was stirred at room temperature for 24 hours to obtain dihydrobenzyl pyromellitate.

The flask is then cooled to 0 ° C. and the solution prepared by dissolving 2.0 g (0.1 mol) ODA in 100 ml NMP in the flask while stirring the solution in the flask.

In addition, a solution prepared by dissolving 45.3 g (0.22 mol) DCC in NMP was dropped into the flask for 25 minutes.

The resulting reaction solution is maintained at 5 ° C. for 4 hours to react and the precipitate formed by filtration under reduced pressure is removed.

The filtrate is then poured into 5 liters of methanol to form a precipitate.

The resulting precipitate is recovered by filtration and immediately dried at 80 ° C. for 14 hours in a vacuum dryer to obtain 47 g polyamic acid ester.

On the other hand, four branched flasks with 100 ml internal volume purged with nitrogen gas were filled with 2.18 g (0.01 mol) PMDA and 10 ml NMP, while 2 g ODA was added to the mixed solution in 10 ml NMP while stirring the mixed solution. The solution prepared by dissolution is dropped.

The resulting reaction solution was held at 5 ° C. for 10 hours and further to obtain a polyamic acid solution.

16.72g polyamic acid ester, 105g NMP, and 5.26g photosensitizer (ie 1,2-naphtho of 2,3,4,4'-tetrahydroxy benzophenone prepared as described above in the polyamic acid solution Quinone diazide-5-sulfonic acid ester (75% average esterification rate) was added.

The mixture was stirred for 3 hours, and the resulting solution was then filtered by a filter having a pore size of 0.5 microns to produce a photosensitive resin composition according to a second specific embodiment of the present invention.

Example 9-17

The photosensitive resin composition according to the second specific embodiment of the present invention was prepared in Example 8 using a polyamic acid derivative, a polyamic acid, and a photosensitizer, while being prepared by mixing the raw materials at the mixing ratio shown in Table 3 described below. It became.

The various properties of the photosensitive resin composition of the second specific example were measured as follows.

Test 4: (resolution measurement)

The resolution of several photosensitive resin compositions prepared in Examples 8-17 was measured as in test 1 performed in Examples 1-5.

Table 4 shows the measurement conditions and the measurement results.

Test 5: (PSG film and adhesive force measurement)

The silicon wafer covered with the PSG film was applied by the photosensitive resin composition prepared in each of Examples 10, 14 and 15 to understand the spin coating method.

Then, a silicon chip having a 2 mm square PSG film formed on the surface is attached to the film so as to be in direct contact with the coated film to form a laminated structure composed of the PSG film on the photosensitive resin composition on the PSG film PSG film of the silicon chip.

The laminate was dried at 90 ° C. for 30 minutes and 150 ° C. for 30 minutes, 250 ° C. for 1 hour and 350 ° C. for 30 minutes to form a polymer film having a thickness of about 5 microns controlled between the silicon wafer and the silicon chip. Firing at

The resulting sample was maintained at 120 ° C. and 2.2 atm for 100 hours in a pressure cooker under steam.

The shear failure strength of a 2mm square silicon chip attached to a silicon wafer was measured for each pressure cooker (PCT) sample and a control sample without PCT.

The results are shown in Table 5.

Test 6: (Epoxy Resin and Adhesion Measurement for Encapsulating Semiconductor)

The silicon wafer covered with the PSG film was applied by the photosensitive resin composition prepared in each of Examples 10, 14 and 15 by the spin coating method.

The sample was then dried at 90 ° C. for 30 minutes and heat treated at 150 ° C. for 30 minutes, 250 ° C. for 1 hour and then 350 ° C. for 30 minutes to form a polymer film with a controlled thickness of about 5 microns.

In addition, silicon wafers having a polymer film formed on the surface were diced into small pieces each 10 mm x 30 mm, and a low pressure transfer molding machine was used to form a resin film encapsulated in 3 mm square in each diced sample.

The epoxy resin for encapsulating the semiconductor device (DE-300TS manufactured by Toshiba Chemical K.K.) was used as the encapsulated resin, and transfer molding was performed for 3 minutes at 175 ° C. temperature and 80 kg / cm ² pressure. .

The resulting sample was maintained for 100 hours in a pressure cooker at 120 ° C. and 2.2 atmospheres of steam.

The shear failure strength of the encapsulated resin was measured in each pressure cooked (PCT) sample and in a non-PCT controlled sample.

The results are shown in Table 5.

The results shown in Tables 4 and 5 show that the polyamide film pattern formed using the photosensitive resin composition according to the second specific embodiment of the present invention showed a suitable adhesive force for using the pattern film as a protective film or an interlayer insulating film in a semiconductor device.

TABLE 3

TABLE 4

d ^* : Developer, TMAH: Aqueous solution (% by weight)

e ^* : P… Positive pattern, N... Voice pattern

TABLE 5

f ^* : Unit (kg / mm ² )

Example 18

16.11 g BTDA and 12.41 g m-hydroxybenzyl alcohol were dissolved in dimethylacetoamide (DMAC) and the reaction was run for 3 hours at 100 ° C. under nitrogen atmosphere to obtain benzyl alcohol ester.

Thereafter, a solution prepared by dissolving 0.62 g bis (γ-aminopropyl) tetramethyl-disiloxane and 9.51 g ODA in 30 ml DMAC was added to the reaction mixture.

A solution prepared by dissolving 20.83 g dicyclohexylcarbodiimide in 30 ml DMAC was also added to the reaction mixture while cooling the solution with ice.

After the dropping was completed, the reaction mixture was stirred for 1 hour while the reaction mixture was cooled with ice, and the reaction mixture was further stirred at room temperature for 10 hours.

After stirring, 5 ml ethanol is added to the reaction mixture, the resulting solution is stirred for 2 hours, followed by filtration to remove insoluble components.

The resulting filtrate is poured into 2 liter methanol to reprecipitate the polymer formed.

The precipitated polymer is isolated by filtration and immediately dried to obtain polyamic acid ester (PE-1), the yield being 55%.

On the other hand four branched flasks with 500 ml internal volume purged with nitrogen gas were filled with 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 100 ml NMP, while cooled on ice.

Then, a solution prepared by dissolving 1.24 g bis (γ-aminopropyl) tetramethyldisiloxane and 19.02 g ODA in 120 ml NMP was added to the mixed solution while stirring the reaction solution so that the temperature of the reaction solution did not exceed 10 ° C. Added slowly.

The reaction solution is continuously stirred for 10 hours while maintaining the temperature dropped in the range between 0 ° C and 5 ° C to obtain a polyamic acid solution (PA-1).

The solution is also prepared by mixing 0.4 g polyamic acid ester (PE-1), 8.56 g polyamic acid solution (PA-1), 0.67 g o-naphthoquinone diazide (QD-5) and 4 g NMP. In order to obtain another photosensitive resin composition according to the second specific embodiment of the present invention, it was filtered by a filter having a pore size of 0.5 micron.

Example 19

21.8 g PMDA was suspended in 200 g ethanol and the suspension was stirred under nitrogen atmosphere for 12 hours under heating at 70 ° C.

The resulting reaction solution was poured into 500 ml water, and the precipitated crystals were separated off by filtration.

The separated crystals were then recrystallized in mixed ethanol solvent / water to get 12 g pyromellitic acid ester.

In the next step the solution was prepared by dissolving 0.37 g bis (γ-aminopropyl) tetramethyldisiloxane, 7.09g 4,4'-diaminodiphenylether, and 9.30 g (0.03 mol) pyromellitic acid ester in 100 ml NMP. It became.

The resulting solution was cooled with ice and then another solution prepared by dissolving 6.30 g dicyclo hexylcarbodiimide in 20 g NMP was added to the resulting solution.

After the addition was completed, the solution was stirred for 12 hours at room temperature, and then 5 ml ethanol was added to the solution.

The resulting solution was stirred for 2 more hours and then the insoluble components were removed by filtration.

The resulting filtrate is poured into 2 liters of water to precipitate the polymer.

The precipitated polymer was thus recovered by filtration and then dried to yield 11 g polyamic acid ester (PE-2) with a yield of 55%.

Thus prepared 2g polyamic acid ester (PE-2) was prepared in Example 18 2g polyamic acid ester (PE-1), 5.35G polyamic acid solution (PA-1), 1g polymer content, 1.25go- It was mixed with naphthoquinone diazide (QD-5) and 6 g NMP, and the resulting solution was filtered by a filter having a pore size of 0.5 microns to prepare a photosensitive resin composition according to a second specific embodiment of the present invention.

Therefore, various properties of the photosensitive resin composition of the second specific example prepared were measured as follows.

[Test 7] (sensitivity measurement)

A silicon wafer of 3 inches in diameter was applied by the photosensitive resin composition prepared in Example 18 by the spin coating method.

The wafer was then heated on a 110 ° C. hotplate for 3 minutes to form a 2.1 micron thick resin composition film.

The resin composition film was exposed to light emitted from the mercury lamp through a quartz mask (i.e., a quartz microphone with 15 different sections over a range between 1% and 75%) to measure sensitivity.

After exposure, the wafer was calcined on a 110 ° C. hotplate for 1 minute and then the wafer was immersed in an alkaline developer (2.38 wt% aqueous solution of TMAH) for 3 minutes to develop to obtain a positive pattern.

1 is a graph showing the sensitivity of the photosensitive resin composition obtained in the above test.

The exposure of light is shown in ordinate 13 and abscissa A, which shows the film residual ratio (ie, the ratio of the thickness of the film after development to the thickness of the film before development) in the exposed portion in FIG.

[Test 8]: (resolution measurement)

A 3 inch diameter silicon wafer was applied by the respective photosensitive resin composition prepared in Examples 18 and 19 by a spin coating method using a spinner, and then the wafer was dried on a hot plate and heated to dry the applied film.

Thereafter, the applied film was exposed to light for 60 seconds through the pattern mask using the above-described exposure apparatus PLA-500F.

After exposure, the film formed of the photosensitive resin composition prepared in Example 19 was subjected to predetermined treatment by placing a wafer on a hot plate.

Thereafter, the silicon wafer was deposited in an alkaline developer (aqueous solution of TMAH) for development, and then the wafer was washed with water.

The cross section of each pattern thus formed was observed by electron microscopy.

The conditions and results of the test are shown in Table 6.

The results shown in Table 6 show that the polyimide film pattern formed using the photosensitive resin composition according to the second specific embodiment of the present invention exhibited a suitable resolution using the pattern as a protective film or an interlayer insulating film in a semiconductor device.

[Test 9]: (resolution measurement)

The silicon wafer is applied by polyamic acid solution (PA-1) and then heated the wafer on a 150 ° C. hotplate for 20 seconds to form a film with a thickness of 1.0 micron.

The film thus formed was applied by the photosensitive resin composition obtained in Example 18, and then the wafer was heated on a 110 ° C. hotplate for 3 minutes to dry to form a resin composition film having a thickness of 5 microns.

Thereafter, the resin composition film was exposed to light through the pattern mask, and then the film was fired for 1 minute on a 110 占 폚 hot plate.

The silicon wafer is also immersed in an alkaline developer (2.38% by weight aqueous solution of TMAH) for 2 minutes to develop, and then the wafer is washed with water.

Thus, the cross section of the formed pattern was observed by electron microscopy.

The resolution of the positive pattern with lines and spaces of 5 microns was recognized (see product J ^* in Table 6).

In this test, a thin polyamic acid film is first formed on a support using a photosensitive resin composition according to a second specific embodiment of the present invention, and then a pattern is formed using the photosensitive resin composition of the present invention.

In this case, the resultant polyimide film pattern is evident as the test result, and exhibits a suitable resolution for using the pattern as a protective film or an interlayer insulating film in a semiconductor device.

[Test 10]: (PSG film and adhesive force measurement)

The adhesive force of the polyimide film pattern was formed under the same conditions as in Test 5 using each of the photosensitive resin compositions prepared in Examples 18 and 19 as the PSG film measured by the above method.

Regarding the photosensitive resin composition prepared in Example 10, the PSG film and the adhesion measurement, which were also covered with the support and under the above conditions, were improved and applied by polyamic acid.

The results of the measurements are shown in Table 7.

[Test 11]: (Measurement of epoxy resin and adhesive force encapsulating semiconductor)

The adhesion of the epoxy resin and polyimide film pattern for encapsulating the semiconductor device was measured under the same conditions and in the test 6 in connection with the respective photosensitive resin compositions prepared in Examples 18 and 19.

Regarding the photosensitive resin composition prepared in Example 18, the measurement applied to the support under the above conditions was also improved and applied by polyamic acid.

The results of the measurements are also shown in Table 7.

The results shown in Table 7 indicate that the polyimide film pattern formed using the photosensitive resin composition according to the second specific embodiment of the present invention exhibits a suitable high adhesion force for using the polyimide film pattern as a protective film or an intermediate film insulating film in a semiconductor device. see.

When the photosensitive resin composition prepared in Example 18 is used, the support is prepared by polyamic acid before formation of the photosensitive resin composition film to improve the adhesion of the resulting polyimide film pattern with an epoxy resin or support for encapsulating the semiconductor device. It is shown that it is desirable to apply.

TABLE 6

d ^* : developer, TMAH aqueous solution (% by weight)

e ^* : P… Positive pattern, N. Voice pattern

i ^* : coating and drying at 110 ° C for 3 minutes (corresponds to test 8)

j ^* : coating and drying at 110 ° C. for 3 minutes (corresponds to test 9)

k ^* : Coating after drying at 90 ° C for 5 minutes and light exposure at 160 ° C for 2 minutes (corresponding to test 8)

l ^* : Coated after drying at 90 ° C for 10 minutes, firing after light exposure at 150 ° C for 1 minute (corresponds to test 8)

TABLE 7

f ^* : Unit (kg / mm ² )

g ^* : The support was applied directly by the photosensitive resin composition.

h ^* : The support was first applied by polyamic acid and then by photosensitive resin composition.

Comparative Example

Four branched flasks purged with nitrogen gas were filled with 20.0 g PMDA, 20.6 g potassium-t-butoxide, and 200 ml tetrahydrofuran (THF) and the system was stirred for 12 hours.

The precipitate formed is then separated by filtration and then washed with THF and diethyl ether followed by drying the washed precipitate.

The dried precipitate was dissolved in 200 ml water, neutralized with dilute sulfuric acid and then the precipitate formed was separated by filtration.

The separated precipitate is also washed with water and soon dried.

Moreover, the dried precipitate was recrystallized from the mixture of ethanol and water to obtain 15 g pyromellitic acid ester.

In the next process, the aforementioned 11.98 g pyromellitic acid ester, 6.01 g ODA, and 8.4 g triethylamine were dissolved in 50 ml NMP and the solution was brought to −10 ° C. in three branched plsks purged with nitrogen gas. Cooled down.

In addition, N, N '-(phenylphosphino) bis [2 (3H) -benzothizolone] was added slowly to the solution, followed by addition of 100 ml NMP to the solution.

The resulting solution was stirred for 2 hours.

After stirring, the solution, poured slowly into 2 liters of methanol, is vigorously stirred to precipitate the polymer, separated by filtration, and then dried in vacuo to yield 10.5 g polyamic acid ester.

The 1 g polyamic acid ester thus prepared is 0.5 g o-naphthoquinone diazide (QD-5), 3 g NMP and 5.35 g polyamic acid solution prepared in Example 18 (PA acting as photoreceptor to prepare a solution) Mixed with -1).

The solution is passed through a filter having a pore size of 0.5 microns to produce a photosensitive resin composition for Comparative Example 1.

On the other hand, the other solution is 8.02 g polyamic acid solution (PA-1), 1.5 g, 0.5 g polyamic acid ester and polymer content prepared in Comparative Example 1, 0.86 g o-naphthoquinone acting as a photosensitizer Diazide (QD-5), and 2 g NMP, are prepared by mixing.

The solution was passed through a filter having a pore size of 0.5 microns to produce a photosensitive resin composition for Comparative Example 2.

It should be noted that in each of Comparative Examples 1 and 2, the organic group having at least one hydroxyl group bonded to the aromatic ring in the photosensitive resin composition was not added in the side chain of the polyamic acid derivative (ie, the resin component of the composition). .

Development, light exposure and coating with an alkaline developer (1.19% by weight aqueous solution of TMAH) were carried out in the test 8 described previously, except for post-exposure, with respect to the photosensitive resin composition for Comparative Examples 1 and 2, respectively. It was run together.

The exposed and unexposed portions of the resin composition layer are both dissolved in the alkaline developer without forming a pattern.

In the photosensitive resin composition of the present invention, it was considered that post-exposure properties of organic groups having at least one hydroxyl group bonded to an aromatic ring were required to form patterns under conditions not added in the side chain of the resin component of the composition.

By the way, the compositions according to Comparative Examples 1 and 2, respectively, were treated as in Test 8, which included postexposure properties.

The resolution of each line and space with a width of 5.0 microns was recognized under these conditions.

Although the organic group having at least one hydroxyl group bonded to the aromatic ring is not added in the side chain of the resin component of the photosensitive resin composition, the post-exposure component shows that the composition forms a pattern.

Example 20

Four branched flasks with 100 ml internal volume purged with nitrogen gas were filled with 1.526 g (0.007 mol PMDA, 1.763 (0.014 mol) 3-hydroxybenzyl alcohol and 10 ml NMP).

The mixed solution is stirred at room temperature for 24 hours to obtain dihydroxybenzyl pyromelli tape.

The flask is then cooled to 0 ° C. and then a solution prepared by dissolving 2.00 g (0.01 mol) 4,4′-diaminodiphenylether in 10 ml NMP is added to the flask while stirring the flask.

In addition, a solution prepared by dissolving 3.17 g (0.0154 mol) DCC in NMP was immersed in the reaction flask over 25 minutes.

The resulting reaction solution is maintained at 5 ° C. to run the reaction for 4 hours, after which time 0.654 g (0.003 mol) PMDA is slowly added to the reaction solution.

In addition, the reaction solution was maintained at 5 ° C. to react for 4 hours, after which the precipitate formed by filtration was removed under reduced pressure.

The filtrate is poured into 600 ml water to precipitate the polyamic acid ester with the copolymer structure.

The 2 g polyamic acid ester thus prepared is dissolved in 8 g NMP, and then 0.46 g photosensitizer (ie 2,3,4,4'-tetrahydroxy) to prepare a photosensitive resin composition according to the third specific embodiment of the present invention. 1,2-naphthoquinone diazide-5-sulfonic acid ester of benzophenone (ie QD-4, 75% average esterification rate) is added to the solution.

Example 21-24

The photosensitive resin composition according to the third specific embodiment of the present invention was prepared as in Example 20 using the raw material composition shown in Table 8.

Example 25

2.0 g polyamic acid ester prepared as in Example 20 was dissolved in 8 g NMP, and then 40 g 2,6-di- as a photosensitive agent in the solution to prepare a photosensitive resin composition according to the third specific embodiment of the present invention. (4'-azidebenzal) -4-methylcyclohexane (A-21) is added (see Table 8).

Example 26

The reaction flask is filled with 16.11 g (0.05 mol) BTDA, 12.41 g 3-hydroxybenzyl alcohol, and 100 g NMP.

The slowly stirred mixture was heated to 90 ° C. and stirring continued at 90 ° C. for an additional 3 hours.

Thereafter, the reaction solution was cooled to room temperature, and then a solution prepared by dissolving 15.02 g (0.075 mol) 4,4'-diaminodiphenyl ester in 70 g NMP was slowly added to the reaction solution.

The reaction solution is then kept at 10 ° C. and a solution prepared by dissolving 21.66 g (0.105 mol) dicyclohexylcarbodiimide in 50 g NMP is dropped into the reaction solution for 30 minutes.

The resulting reaction solution is stirred at 10 ° C. for 4 hours.

In the next step, 5.45 g (0.025 mol) PMDA is added to the reaction solution, and the resulting solution is stirred for 5 hours at a reaction temperature of 10 ° C.

The precipitate, which is a dispersion, is then removed by suction filtration to obtain a mother liquor (ie, a solution of polyimide acid derivatives having a copolymer structure).

In addition, 1.0 g o-naphthoquinone diazide (QD-5) was dissolved in a 20 g polyimide derivative solution, and the resulting solution was 0.5 micron in pore size to prepare a photosensitive resin composition according to the third specific embodiment of the present invention. Pass the filter with (see Table 8).

Therefore, various properties of the photosensitive resin composition of the third specific example prepared were measured as follows.

[Test 12]: (Measurement of resolution)

The resolution of the photosensitive resin composition prepared in each of Examples 20-26 was measured by the same method as in Test 1.

The results and conditions of the measurements are shown in Table 9.

[Test 12 ']: (Measurement of resolution)

A silicon wafer with a diameter of 3 inches was applied by the photosensitive resin composition prepared in Example 26, and then placed in a 90 ° C. hotplate to dry and heat the coating for 10 minutes to obtain a composition film having a thickness of 4 microns. .

The composition film was exposed to ultraviolet radiation with 200 mJ / cm ² exposure through a pattern mask using the exposure apparatus PLA-500F described above.

After exposure, the silicon wafer was calcined for 20 minutes on a 140 DEG C hotplate, and then the silicon wafer was deposited in an alkaline developer (2.38 wt% aqueous solution of TMAH) for 7 minutes at room temperature to develop.

Finally the wafer was washed in water.

The cross section of each pattern thus formed was observed by electron microscopy.

In Table 9 the results and conditions of the measurements are shown.

The results shown in Table 9 show that the polyamide film pattern formed using the photosensitive resin composition of the third specific example showed a suitable resolution for using the pattern as an interlayer insulating film or protective film in a semiconductor device.

TABLE 8

compound reacted with b ^* : a ^*

The description in the specification should be referred to with reference to the abbreviation of the compound in the table.

TABLE 9

d ^* : Developer, TMAH aqueous solution (% by weight)

e ^* : P… Positive pattern, N. Voice pattern

m ^* : post exposure bake at 140 ° C for 20 minutes (corresponds to test 12 ')

Example 27

Polyimide acid (PA-2) having an intrinsic viscosity number of 0.60 g / dl was obtained by reaction in 0.1 mol BTDA, 0.095 mol ODA and 0.005 mol bis (γ-aminopropyl) tetramethylsiloxane.

The solution was then prepared with 7.5 g polyimide acid derivative, 2.5 g polyimide acid (PA-2) described above, and 2.5 g photoresist (i.e., o-naphtho in 50 g NMP) represented by formula (PE-3) given below. Prepared by dissolving the quinone diazide compound (QD-4).

m: n = 0.95: 0.05 ηinh = 0.20

Thus prepared solution is passed through a filter having a pore size of 0.5 microns to obtain a photosensitive resin composition according to a second specific embodiment of the present invention.

[Examples 28 and 29]

The photosensitive resin composition of the present invention was prepared as in Example 27 using the photosensitive agent and resin component shown in Table 10.

[Test 13]: (resolution measurement)

Silicon wafers were applied by polyimide acid solution (T4200T manufactured by Toshiba Chemical Company Limited).

The wafer was then heated on a 160 ° C. hotplate for 20 minutes to obtain a coated film with 0.4 micron thickness.

The applied film was further applied by the photosensitive resin composition prepared in Example 27, and the wafer was heated on a 90 ° C. hotplate for 10 minutes to obtain a composition film having a thickness of 5 microns.

Thereafter, the composition film was exposed to light by an exposure apparatus of 200 mJ / cm ² through a pattern mask, and the wafer was then deposited in an alkaline developer (2.38 wt% aqueous solution of TMAH) for development.

Finally, the wafer was washed in water to form the desired pattern.

Thus, the cross section of the formed pattern was observed by electron microscopy.

The same test was applied to each of the photosensitive resin compositions prepared in Examples 28 and 29 to measure the resolution of the formed pattern.

The results and conditions of the test are shown in Table 10.

[Test 14]: (adhesion measurement)

The silicon wafer was applied with a polyimide acid solution available on the market, and then the wafer was heated to form a film.

The film thus formed was further applied by the photosensitive resin composition prepared in Example 27 as in Test 13 described above.

In addition, the wafer was heated in an oven at 150 ° C. for 30 minutes and 250 ° C. for 30 minutes, and then in an oven at 350 ° C. for 30 minutes to form a cured film.

The cured film was divided by laser cutting lines at 1 mm intervals to form 100 square cross sections each measuring 1 mm x 1 mm.

The cellophane tape attached to the elapsed membrane was peeled off (lateral cutting test).

However, the cured film did not come off at all.

The wafer was then exposed in saturated steam at 12 ° C. (pressure cooker test, PCT).

The wafer was lateral cut again for 100 hours after the pressure cooker test with the result that the film was not recognized at all.

[Test 15]: (PSG film and adhesive force measurement)

Silicon wafers with PSG films formed on the surface were first applied by polyimide acid and then by the photosensitive resin composition prepared in each of Examples 27-29.

Then, a 2 mm square silicon chip having a PSG film formed on the surface and a thin polyimide film formed on the PSG film was formed to form a laminated structure of the PSG film / thin polyimide film / photosensitive resin composition film / thin polyimide film / PSG film. The photosensitive resin composition is placed on the film.

The adhesion of the PSG film and the photosensitive resin composition was measured by the same method under the same conditions as in Test 5.

The results are shown in Table 11.

[Test 16]: (Measurement of epoxy resin and adhesive force for encapsulating semiconductor device)

Silicon wafers having a phosphosilicate glass (PSG) film formed on the surface were first applied by polyimide acid and then by the photosensitive resin composition prepared in each of Examples 27-29.

The epoxy resin and adhesive force for encapsulating the semiconductor device were measured by the same method under the same conditions as in Test 6.

The results are also shown in Table 11.

The results of Tables 10, 11 and Test 14 show that the resulting polyimide film pattern is a protective layer film in a semiconductor device where a thin polyimide acid film is first formed on the support and then a pattern is formed using the photosensitive resin composition of the present invention. Or using a pattern as the interlayer insulating film to show a suitable resolution and adhesion as a whole.

TABLE 10

d ^* : Developer, TMAH: Aqueous solution (% by weight)

e ^* : P… Positive pattern, N... Voice pattern

The description in the specification should be referred to in the Tables with reference to the abbreviations of the compounds.

TABLE 11

f ^* : unit kg / mm ²

The description in the specification should be referred to with reference to the abbreviation of the compound in the table.

Reference Example

2 g o-naphthoquinone diazide compound (QD-4) and 8.0 g polyimide (PI-3) shown below were dissolved in 40 g NMP, and the resulting solution was used to prepare a photosensitive polyimide resin composition. Pass through a filter with a pore size of 0.5 microns.

t: u: v = 80: 10: 10

ηinh = 0.20

The silicon wafer is then applied in the polyamic acid solution useful in the market, namely the aforementioned CT4200T, and then the coating is dried in an oven at 150 ° C. for 1 hour to form a coated film with a thickness of 0.8 microns.

The coated film thus prepared is further applied by the photosensitive polyimide resin composition film described above and then dried and heated on a hot plate for 5 minutes to obtain a resin composition film having a thickness of 5.0 microns.

Thereafter, the resin composition film is exposed to light through a pattern mask, and then the wafer is deposited in an alkaline developer (1.19% aqueous solution of TMAH) for development.

Finally, the wafer is washed in water to obtain a positive pattern.

The pattern thus formed is observed under a microscope.

A resolution of 4 microns of line and space was recognized.

The photosensitive polyimide resin composition was tested for epoxy resin to encapsulate a semiconductor device as in test 16 and for measuring adhesion and for phosphosilicate glass and for adhesion as in test 15.

The result obtained in the above test was not better than under the conditions using the photosensitive resin composition of the present invention.

The test results show that it is possible to form satisfactory polyimide film patterns under conditions using various photosensitive compositions, including those that do not fall within the technical scope of the present invention where the support has been improved and applied by a polyimide acid solution. .

As described above, the photosensitive resin composition according to any one of the third specific embodiments of the present invention can simplify the process of forming a polyimide film pattern without using a resist and forming a polyimide film pattern in the manufacture of a semiconductor device. Make it possible.

It should also be noted that the polyimide film pattern formed using the composition of the present invention exhibits a suitable resolution, adhesive force, etc. for use of the pattern as a protective film or an interlayer insulating film in a semiconductor device.

The following examples illustrate specific methods of forming polyimide film patterns using photosensitive resin compositions according to four specific examples of the present invention.

The abbreviations used in Examples 30-61 and Tables 12-19 that follow are described in Tables G and H.

Example 30

Nitrogen gas dried by phosphorous pentoxide was added into the reaction flask with a stirrer, thermometer and dropping funnel.

The reaction flask was then 4.635 g (0.21 mol) pyromellitic dianhydride 19.993 g (0.062 mol) 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 0.333 g (0.003 mol) maleic anhydride and 100 g N -Filled with methyl-2-pyrrolidone.

The resulting mixture is thoroughly stirred and then cooled to -5 ° C.

Then 15.996 g (0.081 mol) 4,4'-diaminodiphenyl ether and 1.199 g (0.003 mol) bis (γ-aminopropyl) tetramethyldisiloxane were dissolved in 69 g N-methyl-2-pyrrolidone. The prepared solution is slowly dropped into the reaction flask.

The mixed solution thus prepared is maintained at a temperature dropped to a range between −5 ° C. and 0 ° C. for 4 hours, after which the reaction is carried out at room temperature (20 ° C.) for 4 hours to obtain polyimide acid.

The mixed solution of polyimide acid and N-methyl-2-pyrrolidone thus prepared are controlled and the algebraic viscosity is measured at 30 ° C. in the mixed solution, resulting in 0.83 dl / g.

In the next process, a 10 g polyimide acid solution is mixed with a 2.5 g naphthoquinone diazide compound of the general formula given below and the mixture is sufficiently stirred at room temperature (20 ° C.) to form a homogeneous system.

The homogeneous mixture is passed through a semipermeable membrane filter having a pore size of 0.5 microns to obtain a photosensitive resin composition containing the naphthoquinone diazide compound and the polyimide acid main component.

The polyimide film pattern was thus formed by the method of forming the special pattern of the present invention using the photosensitive resin composition thus prepared, and various properties of the polyimide film pattern were measured as follows.

[Test 17]: (resolution measurement)

A silicon wafer with a diameter of 3 inches was applied by the photosensitive resin composition prepared in Example 30 using a spinner, and then the wafer was heated on a 100 ° C. hotplate for 10 minutes to form a resin film having a thickness of 6.2 microns. .

The resin film thus formed had an exposure of 70 mJ / cm ² (365 mm wavelength) and was exposed to light through a quartz mask for resolution testing using a contact exposure machine ((A-800) manufactured by COBIET INC.). Exposed.

After the exposure process, the firing was applied to the resin film at 150 ° C. for 2 minutes, followed by immersing the wafer in a 60 seconds pattern resistive developer (2.38 wt% aqueous solution of tetramethyl ammonium hydroxide) and then 20 to form a negative pattern. Wash in water for seconds.

Thus, the cross section of the formed pattern was observed by electron microscopy.

A resolution of 3 micron line and space was recognized.

The resulting pattern was heated at 320 ° C. to form a satisfactory polyimide film pattern.

[Test 18]: (Measurement of Silicon Wafer and Adhesive Force)

Silicon wafers with a 3 inch diameter were applied by the photosensitive resin composition prepared in Example 30 using a spinner.

The wafer was heated on a 90 ° C. hotplate for 10 minutes to form a resin film with a 5.0 micron thickness.

The wafer is then placed in a dryer at a constant temperature and heated at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and soon 320 ° C. for 1 hour to imidize the resin layer formed on the wafer.

In addition, the wafer was heated at 120 ° C. for 24 hours under saturated steam at 2 atmospheres, and then the adhesive force was measured by a checker test method.

It is known that a resin layer does not peel at all from a wafer and shows the high adhesive force of a wafer and a resin layer.

[Test 19]: (thermal resistance measurement)

Silicon wafers with a 3 inch diameter were applied by the photosensitive resin composition prepared in Example 30 using a spinner.

The wafer was heated on a 90 ° C. hotplate for 10 minutes to form a resin layer with a thickness of 5 microns.

The wafer is then placed in a dryer at a constant temperature to imidize the resin layer formed on the wafer, and heated at 150 ° C. for 1 hour, 250 ° C. for 1 hour, and then 320 ° C. for 1 hour.

After heating, the resin layer was peeled off the wafer by a laser followed by peeling the resin layer by thermogravimetric analysis (TGA).

The weight loss due to pyrolysis is not recognized up to about 400 ° C.

Comparative test to measure properties

Silicon wafers with a diameter of 3 inches were applied by the photosensitive resin composition prepared in Example 30 using a spinner.

The wafer was heated on a 90 ° C. hotplate for 10 minutes to form a resin layer with a 5.0 micron thickness.

The resin layer thus formed was then exposed to light through a quartz mask for resolution testing using the aforementioned contact exposure machine CA-800 with an exposure of 70 mJ / cm ² (365 mm wavelength length).

After the exposure process, the silicon wafer was immediately deposited in a resistive developer (2.38 wt% aqueous solution of tetramethyl ammonium hydroxide) for 60 seconds to form a pattern.

Thereafter, the silicon wafer was removed from the developer and washed with water for 20 seconds.

Under the above conditions, however, it was found that the remaining portion of the patterned resin film was dissolved without forming a good pattern.

On the other hand, a silicon wafer having a diameter of 3 inches was applied by the photosensitive resin composition prepared in Example 30 using a spinner.

The wafer was heated on a 90 ° C. hotplate for 10 minutes to form a resin film with a thickness of 5.0 microns.

Thereafter, the resin film thus formed was heat-treated at 150 ° C. for 2 minutes, and then through a quartz mask to measure the resolution using the aforementioned contact exposure machine CA-800 with 70 mJ / cm ² light exposure (365 nm wavelength length). The resin film was exposed to light.

After the immediate exposure process, the silicon wafer was deposited in a resist developer (2.38 wt% aqueous solution of tetramethyl ammonium hydroxide) for 60 seconds without forming a pattern.

Pattern formation was considered to be achieved because the naphthoquinone diazide compound contained in the resin layer was decomposed during the heat treatment prior to the exposure process.

Example 31-38

The polyimide acid solution was prepared as in Example 30 using the raw material composition shown in Table 12.

In Table 12 the logarithmic viscosity of each polyimide acid solution prepared in Examples 31-38 is also shown.

In addition, the photosensitive resin composition of Examples 31-38 was prepared by mixing a predetermined amount of a naphthoquinone diazide compound and a polyimide acid solution as shown in Table 12.

[Test 20]: (resolution measurement)

The layers of the photosensitive resin composition prepared in each of Examples 31-38 formed on the silicon wafer were developed and baked by the same conditions and methods as in Test 17 to measure the resolution for Example 30 to form a pattern. , And light exposure.

The cross section of each pattern thus formed was observed by electron microscopy to measure the resolution.

The results are shown in Table 13.

[Test 21]: (silicon wafer and adhesive force measurement)

The adhesion between the formed pattern and the silicon wafer was measured by the above method under the same conditions as in Test 18 for measuring the adhesion for Example 30 with respect to the photosensitive resin composition prepared in each of Examples 31-38.

The results are shown in Table 13.

[Test 22]: (thermal resistance measurement)

The thermal resistance of the pattern formed on the silicon wafer was measured by the same method under the same conditions as in Test 19 to measure the thermal resistance for Example 30 with respect to the photosensitive resin composition prepared in each of Examples 31-38. .

The results are shown in Table 13.

As shown in Table 13, the negative pattern was formed under the conditions using the photosensitive resin composition prepared in any one of Examples 31-38.

In particular, the pattern formed using the composition prepared in any one of Examples 31-36 is excellent in resolution, exhibits high adhesion between the formed pattern and the support, and is sufficiently high in heat resistance.

When the composition prepared in Example 37 is used, on the other hand, a large amount of the naphthoquinone diazide compound is used, the weight loss of the resin film becomes large in the imidization step, and the adhesion between the support and the resulting polyimide film becomes small.

On the other hand, under the conditions of the composition prepared in Example 38, on the other hand, the amount of naphthoquinone diazide used is small, and the resolution of the formed pattern is relatively high in solubility in each exposed and unexposed portion in alkaline solution. Because it is high, it becomes somewhat small. Of course, the thirty-eighth embodiment has poor pattern characteristics than the other embodiments.

TABLE 12

TABLE 13

* Measurement by checker test: Silicon wafer and adhesive force after heating for 24 hours under 2 atmosphere of saturated steam

(Adhesion measurement)

* 10% weight loss temperature (℃): TGA measurement after thermosetting at 320 ℃

Heat resistance measurement

Example 39-45

The polyimide acid solution used in Examples 39-45 was prepared as in Example 30 using the raw material compositions shown in Table 14.

Table 14 also shows the algebraic viscosity of each polyimide acid solution described.

In addition, the photosensitive resin composition for Examples 39-45 was prepared by mixing a predetermined amount of a naphthoquinone diazide compound and a polyimide acid solution as shown in Table 14.

[Test 23]: (resolution measurement)

Films of the photosensitive resin composition prepared in each of Examples 39-45 formed on the silicon wafer were developed, calcined, and treated under the same conditions as in Test 17 to measure the resolution for Example 30 to form a pattern, and Light exposure.

In this test, the exposure was set at 150 mJ / cm ² and the development was immersed of silicon wafer in an aqueous solution containing 1.19 wt% tetramethyl ammonium hydroxide, followed by washing the wafer in water.

The cross section of each pattern thus formed was observed by electron microscopy to measure the resolution.

The results are shown in Table 15.

[Test 24]: (silicon wafer and adhesive force measurement)

The adhesion between the formed pattern and the silicon wafer was measured under the same conditions as in Test 18 and by the method to measure the adhesion to Example 30 with respect to the photosensitive resin composition prepared in each of Examples 39-45.

The results are also shown in Table 15.

[Test 25]: (thermal resistance measurement)

The thermal resistance of the pattern formed on the silicon wafer was measured under the same conditions as in Test 19 and by the method for measuring the thermal resistance for Example 30 with respect to the photosensitive resin composition prepared in each of Examples 39-45.

The results are also shown in Table 15.

As shown in Table 15, a good pattern of positive or negative is formed under the conditions using the photosensitive resin composition prepared in any one of Examples 39-45.

The pattern formed using the composition prepared in any one of Examples 39-45 exhibits high adhesion between the formed pattern and the support and the heat resistance is sufficiently high.

With the composition prepared in each of Examples 39-44, it was found that the formed pattern showed very high adhesion with the silicon wafer in the test to measure the silicon wafer and adhesion.

In particular, even after heating at 120 ° C. for 62 hours, the formed pattern did not peel off at all in the water.

On the other hand, peeling does not occur at all even after the composition prepared in Example 45 is heated at 120 ° C. for 24 hours under conditions.

However, it was found that the pattern formed peeled 10% in water after heating for 62 hours.

Under conditions using a polyfunctional naphthoquinone diazide sulfonic acid ester as the photosensitizer as in Example 45, it is considered that the unreacted naphthoquinone diazide sulfonic acid ester is crosslinked during the heat treatment to lower the plasticity of the resin layer. do.

Under conditions using a monofunctional naphthoquinone diazide sulfate ester as the photosensitizer as in Examples 39-44, however, the above-mentioned crosslinking does not occur, and as mentioned above, the crosslinking leads to excellent adhesion of the pattern formed with the wafer. .

Comparative test to measure characteristics

The resin film was formed on the silicon wafer using the photosensitive resin composition prepared in Example 39, and then the resin layer was exposed to light as in Test 23 described above.

Immediately after exposure to light, the silicon wafer is deposited in a resistance developer (1.19 wt% aqueous solution of tetramethyl ammonium hydroxide).

It is possible to form a pattern.

However, when the wafer was taken out in the developer and washed with water for 30 seconds, the remaining portion of the resin layer which did not form a satisfactory pattern was dissolved.

TABLE 14

TABLE 15

* Measurement by checker test: Silicon wafer and adhesive force after heating for 62 hours under 2 atmosphere of saturated steam

(Adhesion measurement)

* 10% weight loss temperature (℃): TGA measurement after thermosetting at 320 ℃

Heat resistance measurement

Example 46-52

The polyamic acid solution used in Examples 46-52 was prepared as in Example 30 using the raw material composition in Table 16.

The logarithmic viscosity of each polyamic acid solution thus prepared is also shown in Table 16.

Thereafter, the photosensitive resin composition for Examples 46-52 was prepared by mixing a predetermined amount of the naphthoquinone diazide compound and thus prepared polyamic acid solution as shown in Table 16.

[Test 26]: (Measurement of resolution)

Films of the photosensitive resin composition prepared in each of Examples 46-52 formed on silicon wafers were developed, baked, and treated by the same conditions and methods as in Test 17 to measure the resolution for Example 30 to form a pattern. And light exposure.

In this test, exposure was set at 170 mJ / cm ² , and development was carried out by immersing the wafer in an aqueous solution containing 1.19 wt% tetramethyl ammonium hydroxide, followed by washing the wafer with water.

The cross section of each pattern thus formed was observed by electron microscopy to measure the resolution.

The results are shown in Table 17.

[Test 27]: (Measurement of silicon wafer and adhesive force)

The adhesion between the formed pattern and the silicon wafer was measured by the method and under the same conditions as in Test 18 to measure the adhesion to Example 30 in relation to the photosensitive resin composition prepared in each of Examples 46-52.

The results are also shown in Table 17.

[Test 28]: (thermal resistance measurement)

The pattern formed on the silicon wafer was measured by the method and under the same conditions as in Test 19 to measure the thermal resistance for Example 30 with respect to the photosensitive resin composition prepared in each of Examples 46-52.

The results are also shown in Table 17.

As shown in Table 17, the negative superior pattern was formed under the conditions of forming the pattern by the above-described method using the photosensitive resin composition prepared in any one of Examples 46-52.

The pattern thus formed shows high adhesion between the pattern formed and the support, and has a sufficiently high thermal resistance.

In Examples 45-52, polyfunctional naphthoquinone diazide sulfate esters were used as photosensitizers.

However, it has been found that the formed pattern exhibits very high adhesion with the silicon wafer.

In particular, even after heating at 120 ° C. for 62 hours, the pattern formed did not peel off at all.

Although the naphthoquinone diazide sulfate ester is crosslinked during the heat treatment, the decrease in plasticity of the resin film is due to the fact that the naphthoquinone diazide sulfonic acid ester used in Examples 46-52 may be mixed with the fatty hydrocarbon structure or the polysiloxane structure in the main chain. It is reasonably considered to have the same soft segment.

Particularly excellent adhesion of the silicon wafer and the formed pattern is possible under conditions where a naphthoquinone diazide sulfate ester having a soft segment such as a fatty hydrocarbon structure, a polysiloxane structure, or a polysilane structure is used as a photosensitive agent.

Comparative test to measure characteristics

The resin film was formed on the silicon wafer using the photosensitive resin composition prepared in Example 46, and then the resin film was exposed to light as in Test 26 described above.

Immediately after exposure, the silicon wafer is deposited in a resistive developer (1.19 wt% aqueous solution of tetramethyl ammonium hydroxide).

It was possible to form a pattern.

However, when the wafer was taken out of the developer and then washed in water for 30 seconds, the remaining portion of the resin layer in which a satisfactory pattern was not formed dissolved.

TABLE 16

TABLE 17

* Measurement by checker test: Silicon wafer and cohesive strength after heating for 2 hours at 2 atmospheres of saturated steam

(Adhesion measurement)

* 10% weight loss temperature (℃): TGA measurement after thermosetting at 320 ℃

Heat resistance measurement

Example 53-61

The polyamic acid solution used in Examples 53-61 was prepared as in Example 30 using the raw material compositions shown in Table 18.

The logarithmic viscosity of each polyamic acid solution thus prepared is also shown in Table 18.

Thereafter, the photosensitive resin composition for Examples 53-61 was prepared by mixing a predetermined amount of the naphthoquinone diazide compound and thus prepared polyamic acid solution as shown in Table 18.

[Test 29]: (Measurement of resolution)

Films of the photosensitive resin composition prepared in each of Examples 53-61 formed on silicon wafers were developed, prescribed treatment, and under the same conditions as in Test 17, to measure the resolution for Example 30 to form a pattern. And light exposure.

In this test, the light exposure amount was set at 150 mJ / cm ² (wavelength 365 nm wavelength), and the development was performed by immersing the silicon wafer in an aqueous solution containing 1.19 wt% tetramethyl ammonium hydroxide, and then wafers were removed by water. Wash.

The cross section of each pattern thus formed was observed by electron microscopy to measure the resolution.

The results are shown in Table 19.

[Test 30]: (Measurement of Silicon Wafer and Adhesive Force)

The adhesion between the formed pattern and the silicon wafer was measured under the same conditions as in Test 18 and by the method to measure the adhesion to Example 30 in connection with the photosensitive resin composition prepared in each of Examples 53-16.

The results are shown in Table 19.

[Test 31]: (Thermal resistance measurement)

The thermal resistance of the pattern formed on the silicon wafer was measured under the same conditions as in Test 19 and by the method to measure the thermal resistance for Example 30 in connection with the photosensitive resin composition prepared in each of Examples 53-61.

The results are also shown in Table 19.

As shown in Table 19, a good pattern of negative was formed under the conditions of forming a pattern by the method described above using the photosensitive resin composition prepared in any one of Examples 53-61.

Therefore, the formed pattern exhibits high adhesive force between the formed pattern and the support, and has a sufficient thermal resistance.

TABLE 18

TABLE 19

* Measurement by checker test: Silicon wafer and adhesive strength after heating for 62 hours under 2 atmosphere of saturated steam

(Adhesion measurement)

* 10% weight loss temperature (℃): TGA measurement after thermosetting at 320 ℃

(Heat resistance measurement)

As described above in detail, the method of the present invention for forming a polyimide film pattern constitutes a predetermined treatment after the light exposure process, and makes it possible to easily form a pattern of high resolution by alkaline developer and development.

The method of the present invention also easily forms a good polyimide film pattern having high adhesion by the semiconductor support and excellent thermal resistance.

The present invention has a high industrial value.

TABLE B

TABLE C

TABLE D

TABLE E

TABLE F

TABLE G

Tetracarboxylic dianhydride

<Photoresist>

Same as those shown in Tables A to D

TABLE H

BDPA: 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride

BTDA: 3,3 ', 4,4'-benzopinone tetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

DPE: 4,4'-diaminodiphenyl ether

DAM: 4,4'-diaminodiphenylmethane

ASi-a (bis (γ-aminopropyl) tetramethyldisiloxane

Asi-b

A: Aniline

T: o-toluidine

A-a: phthalic anhydride

A-b: Hexahydrophthalic anhydride

A-c: Methylnadic Anhydride

A-d: 4-methylhexahydrophthalic anhydride

A-e: Male Anhydride

From (PAC-a) to (PAC-q)

Additional advantages and modifications will readily occur to those of ordinary skill in the art.

As a result, the invention in its broader aspects is not limited to the specific details and illustrated embodiments described and described herein.

Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their corresponding claims.

Claims (10)

The repeating unit represented by the following general formula (I) (Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group and R ³ and R ⁴ represent a monovalent organic group, or have at least one hydroxyl group or hydroxyl group bonded to an aromatic ring, At least one of R ³ and R ⁴ is an organic group). The photosensitive resin composition for forming a polyimide film pattern, comprising a polyamic acid derivative and a photosensitive agent. Polyamic acid derivative which has a repeating unit represented by following General formula (1), Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group, R ³ and R ⁴ represent a monovalent organic group, or have at least one hydroxyl group or hydroxyl group bonded to an aromatic ring , At least one of R ³ and R ⁴ is the organic group) Repeating unit represented by the following general formula (2) A photosensitive resin composition for forming a polyimide film pattern, characterized in that it is composed of a polyamic acid and a photosensitizer having R ⁵ is a tetravalent organic group, and R ⁶ represents a divalent organic group. Repeating unit represented by the following general formula (1) and Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group, R ³ and R ⁴ represent a monovalent organic group, or has at least one hydroxyl group or hydroxyl group bonded to an aromatic ring, and R At least one of ³ and R ⁴ is the organic group) Repeating unit represented by the following general formula (2) (Wherein R ⁵ represents a tetravalent organic group and R ⁶ represents a divalent organic group) and a photosensitive material for forming a polyimide film pattern, comprising a polyamic acid derivative having a copolymer structure and a photosensitizer Resin composition. The photosensitive resin composition for forming a polyimide film pattern according to any one of claims 1, 2 and 3, wherein the photosensitive agent is an o-quinone diazide compound. The photosensitive resin composition according to any one of claims 1, 2 and 3, wherein the photosensitive agent is an azide compound. In the method for forming a polyimide film pattern, (a) a photosensitive resin composition composed of a polyamic acid derivative having a repeating unit represented by the following general formula (1) and a photosensitive agent, (b) to the general formula (1) A polyamic acid derivative having a repeating unit represented by the following, a photosensitive resin composition composed of a polyamic acid having a repeating unit represented by the following general formula (2) and a photosensitive agent, and (c) represented by the following general formula (1) Supports a resin layer containing, as a main component, at least one substance selected from the group consisting of a photosensitive resin composition composed of a polyamic acid derivative having a copolymer structure comprising a repeating unit and a repeating unit represented by the following general formula (2): Formed on the phase, Wherein R ¹ represents a ^tetravalent organic group, R ² represents a divalent organic group, R ³ and R ⁴ represent a monovalent organic group or a hydroxyl group, and at least one of R ³ and R ⁴ is bonded to an aromatic ring An organic group having a hydroxyl group of R ⁵ is a tetravalent organic group and R ⁶ is a divalent organic group; Selectively exposing a predetermined region of the resin layer to light; Developing the resin layer after photoexposure to selectively remove or leave the predetermined region of the resin layer; A method of forming a polyimide film pattern, comprising the step of heating the developed resin layer to imidize the resin layer. The polyamide according to claim 6, further comprising before the step of forming a resin layer containing at least one substance as a main component with a main component selected from the group consisting of the photosensitive resin compositions (a), (b) and (c). Forming a thin film of acid, wherein said polyimide film pattern is formed. The method of forming a polyimide film pattern according to claim 6, wherein the firing treatment is applied to the resin layer at 90 to 200 DEG C after the light exposure step and the developing treatment is applied to the screw resin layer. The polyamic acid which has a repeating unit by following General formula (2) in the method of forming a polyimide membrane pattern. (Wherein R ⁵ is a tetravalent organic group and R ⁶ represents a divalent organic group) and a resin layer containing a naphthoquinone diazide compound as a main component is formed on a support; Optionally exposing a predetermined region of the resin layer to light; Firing at 130-200 ° C. to the resin layer after light exposure; Developing the resin layer after the firing treatment to selectively remove or leave the pre-determined region of the resin layer; A method of forming a polyimide film pattern, comprising the step of heating the developed resin layer to imidize the resin layer. The method for forming a polyimide film pattern according to claim 9, wherein the naphthoquinone diazide compound contained in the resin layer is 1,2-naphthoquinone diazide-4-sulfonic acid ester.