KR20150102467A - Photosensitive polyimide resin, composition including the same and method for forming polymer membrane using the same - Google Patents

Abstract

Disclosed are a photosensitive polyimide resin which can easily form a pattern having a high resolution by using a chemically amplified positive-type photosensitive polyimide resin, a composition including the same, and a method for forming a polymer membrane by using the same. The photosensitive polyimide resin includes a recurring unit represented by Chemical Formula 1. In Chemical Formula 1, X and R are the same or different from each other, wherein X is an organic group including an aromatic ring compound, and R is an organic group including or non-including an aromatic ring compound, or an inorganic group non-including an aromatic ring compound. Y is a leaving group coupled with an oxygen atom of a hydroxy group included in X or R and capable of being separated by oxygen, which is a C1 to 20 hydrocarbon group including 1 to 10 oxygen atoms. a, b, c, and d are the number of Y, wherein each of the a, b, c, and d are integers of 0 to 4, and the sum of the a, b, c, and d is 1 or greater.

Description

TECHNICAL FIELD The present invention relates to a photosensitive polyimide resin, a composition containing the same, and a method for forming a polymer membrane using the same.

The present invention relates to a photosensitive polyimide resin, a composition containing the photosensitive polyimide resin, and a method of forming a polymer film using the same. More particularly, the present invention relates to a photosensitive polyimide resin which facilitates the formation of a pattern having a high resolution A composition containing the same, and a method of forming a polymer membrane using the same.

Resins typified by polyimide or polybenzoxazole have excellent heat resistance and electrical insulation and are used for a surface protective film of semiconductor devices, an interlayer insulating film, and an insulating layer of an organic electroluminescent device. In recent years, as circuit patterns of semiconductors and display devices have become finer, a high resolution of several mu m is required for a surface protective film, an interlayer insulating film, and the like. Accordingly, a composition using a positive photosensitive polyimide resin, A composition using a cazole resin is widely used.

In the conventional interlayer insulating film, polyamic acid (PAA) as a polyimide precursor or polyhydroxyl amide (PHA) as a precursor of polybenzoxazole is spin-coated on a base such as a silicon wafer in order to improve workability A film is formed, followed by exposure and development to form a pattern, followed by curing at a high temperature of about 300 DEG C or higher for a certain period of time. However, in recent years, in order to improve the productivity of semiconductors, the aim is to shorten the temperature rise time, and in particular, a low curing temperature of the mounting materials is required due to the miniaturization of chips due to the highly integrated semiconductor production.

Examples of the photosensitizer used in the conventional positive photosensitive resin composition include a naphthoquinone diazide sulfonic acid ester compound and the like, a composition containing an alkaline soluble resin and a phenol naphthoquinone diazide sulfonic acid ester compound, A positive type photosensitive resin composition containing a heat resistant resin precursor, a quinone diazide compound, a compound containing an alkoxymethyl group, and a solvent has been newly proposed, but there is a limit to use as a composition having a high resolution.

Accordingly, an object of the present invention is to provide a photosensitive polyimide resin, a composition containing the same, and a method of forming a polymer film using the photosensitive polyimide resin, which can not only shorten the time of the curing process during semiconductor manufacturing but also can be cured at low temperatures.

Another object of the present invention is to provide a photosensitive polyimide resin, a composition containing the same, and a method of forming a polymer film using the same, which can improve the resolution of the lithography process.

In order to achieve the above object, the present invention provides a photosensitive polyimide resin comprising a repeating unit represented by the following general formula (1).

 [Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which is bonded to an oxygen (O) atom of a hydroxyl group contained in X or R and can be separated by an acid, and is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms A, b, c, and d are the numbers of Y, and each is an integer of 0 to 4. The sum of a, b, c, and d is 1 or more.

Further, the present invention provides a composition comprising a photosensitive polyimide resin, a binder resin, a photoacid generator, and the remaining solvent, which contains a repeating unit represented by the following formula (1).

[Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which can be bonded to the oxygen atom of the hydroxy group contained in X or R and can be separated by an acid, is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms, and a, b, c and d are the numbers of Y, and each is an integer of 0 to 4, and the sum of a, b, c and d is 1 or more.

The present invention also provides a method of manufacturing a semiconductor device, comprising: forming a film by applying a composition containing the photosensitive polyimide resin on a semiconductor substrate; Exposing the film with an exposure mask and an exposure machine; Developing with a developer to form a pattern; And a curing step for removing the solvent, wherein the composition comprising the photosensitive polyimide resin comprises a photosensitive polyimide resin comprising a repeating unit represented by the following formula (1), a binder resin, a photoacid generator, and the remaining solvent A polymer film forming method is provided.

 [Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which can be bonded to the oxygen atom of the hydroxy group contained in X or R and can be separated by an acid, is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms, and a, b, c and d are the numbers of Y, and each is an integer of 0 to 4, and the sum of a, b, c and d is 1 or more.

The photosensitive polyimide resin, the composition including the same, and the polymer film forming method using the photosensitive polyimide resin according to the present invention are characterized in that since the chemical preimidization reaction is completed when the photosensitive polyimide resin is produced, And it is possible to perform low-temperature curing at 200 DEG C or lower only for removing the solvent. Further, by introducing a leaving group which is easily separated by an acid generated by the photoacid generator, the resolving power of the lithographic process can be improved.

Hereinafter, the present invention will be described in detail.

The photosensitive polyimide resin according to the present invention comprises a repeating unit represented by the following general formula (1).

[Chemical Formula 1]

In the above formula (1), X and R are the same or different, and X is an organic group containing an aromatic ring compound, preferably an aromatic hydrocarbon group having 6 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, (-OH), a carbonyl group, an amine group, SO _2, or CF ₃ , which may contain 1 to 20 heteroatoms such as sulfur (S), oxygen (O) and fluorine (F) _And R may be an organic group containing no aromatic ring compound or an organic group containing no aromatic ring compound, preferably an aromatic group having 6 to 40 carbon atoms, more preferably a linear group having 6 to 35 carbon atoms , A branched and / or aromatic hydrocarbon group, and may optionally contain 1 to 20 hetero atoms such as sulfur, oxygen and fluorine, for example, a hydroxyl group, a carbonyl group, an amine group, an SO ₂ or CF _3, etc. And Y is an acid labile group which is bonded to an oxygen (O) atom of a hydroxyl group (-OH) contained in X or R and can be separated by an acid, A, b, c and d represent the number of Y atoms, preferably 1 to 5 carbon atoms, and a, b, c and d represent hydrocarbon groups containing 1 to 10 carbon atoms, Each of which is an integer of 0 to 4, and the sum of a, b, c and d is 1 or more. On the other hand, the weight average molecular weight (Mw) of the photosensitive polyimide resin represented by Formula 1 is 1,000 to 200,000, preferably 3,000 to 20,000, and more preferably 5,000 to 10,000.

,

,

,

,

,

,

,

,

,

,

,

및

등이 있으며(상기 예시들에서 굴곡선(

)은 연결부(connecting bond)를 나타낸다), 상기 예시들에 나타낸 바와 같이, 헤테로 원자가 포함될 경우에는, 방향족 고리 혹은 방향족 고리의 사이 등에 위치할 수 있다.
Specific examples of X in the above formula (1)

,

,

,

,

,

,

,

,

,

,

,

And

And the like (in the above examples,

Refers to a connecting bond), as shown in the above examples, when a hetero atom is included, it may be located between an aromatic ring or an aromatic ring or the like.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, 및

등이 있으며(상기 예시들에서 굴곡선(

)은 연결부를 나타낸다), 상기 예시들에 나타낸 바와 같이, 헤테로 원자가 포함될 경우에는, 방향족 고리 혹은 방향족 고리의 사이 등에 위치할 수 있다.
Specific examples of R in the above formula (1)

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, And

And the like (in the above examples,

) Represents a connecting part), as shown in the above examples, when a hetero atom is included, it may be located between an aromatic ring or an aromatic ring or the like.

In the examples of X and R, when the hydroxy group (-OH) is present, the oxygen atom of the hydroxy group may be bonded to Y, and when no hydroxy group is present, Y does not exist. Therefore, the sum of a, b, c, and d in Formula 1 should be at least 1, and therefore one of X and R must contain at least one hydroxy group.

,

,

,

,

,

및

등의 Y가 상기 화학식 1의 X 또는 R에 포함되는 히드록시기의 산소 원자에 결합하여 아세탈이 되는 것이 가장 바람직하다(상기 예시들에서 굴곡선(

)은 연결부를 나타낸다).
Y is an acid labile group which can be separated by an acid generated by a photoacid generator and is bonded to an oxygen atom of a hydroxyl group contained in X or R of the formula 1 And the hydrogen (H) atom of the hydroxyl group is removed), acetal group, ketal group, carbonate group and ester group,

,

,

,

,

,

And

It is most preferred that Y is bonded to the oxygen atom of the hydroxy group contained in X or R of formula 1 to form an acetal (in the above examples,

) Represents a connection portion).

) 화합물을 첨가한 후, 일정 온도로 유지시켜 제조할 수 있다.
On the other hand, the photosensitive polyimide resin represented by the above-mentioned formula (1) is allowed to react at -30 to 200 占 폚, preferably 0 to 100 占 폚, in a solvent such as N-methyl-2-pyrrolidone or gamma-butyrolactone Condensation reaction of a diamine compound and a dianhydride compound for 2 to 24 hours, preferably for 2 to 12 hours, more preferably for 2 to 8 hours at a temperature of 25 to 80 ° C, more preferably 25 to 80 ° C, , A polyimide precursor is synthesized and then a catalyst such as acetic anhydride and pyridine is continuously added to synthesize a polyimide imidized by a chemical imidization reaction and then a Y A saturated or unsaturated hydrocarbon group of 2 to 30 carbon atoms containing 1 to 20 oxygen atoms, preferably a saturated or unsaturated hydrocarbon group of 4 to 20 carbon atoms containing 1 to 15 oxygen atoms Compounds containing saturated ether groups, such as ethyl vinyl ether (EVE,

) Compound and then keeping it at a constant temperature.

In the following Reaction Scheme 1, an example in which the photosensitive polyimide resin represented by Formula 1 is prepared is shown.

[Reaction Scheme 1]

(H ₂ O) composed of two hydrogen atoms in the amine group of the diamine and an oxygen atom (oxygen atom located between the carbonyl group) of the dianhydride by the condensation reaction of the diamine and the dianhydride, The molecules are separated and the imidized polyimide is synthesized by removing the two hydrogen atoms and leaving the remaining nitrogen atoms at positions where the oxygen atoms of the dianhydrides are located by the chemical imidization reaction. Subsequently, a compound represented by Y in the above formula (1) is bonded to the hydroxyl group (precisely, an oxygen atom) of the imidized polyimide to form an acetyl group, thereby preparing a photosensitive polyimide resin.

Representative examples of the monomer constituting the diamine compound include the compounds represented by the following general formulas (2a) to (2e).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

Representative examples of the monomers constituting the dianhydride compound include the compounds represented by the following formulas (3a) to (3e).

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

On the other hand, if necessary, the end of the photosensitive polyimide resin represented by the above formula (1) (the amine group in which the condensation reaction and the chemical imidization reaction have not occurred) can be reacted with the sealing agent, , The dissolution rate of the photosensitive polyimide resin to the aqueous alkaline solution can be controlled by sealing the end of the photosensitive polyimide resin with a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group. The sealing agent may be a monoamine, an acid anhydride, an acid chloride, or a monocarboxylic acid having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group, Is 10 to 60 mol%, preferably 5 to 50 mol%, based on 100 mol% of the total amines contained in the polyamide resin.

The composition comprising the photosensitive polyimide resin according to the present invention comprises a photosensitive polyimide resin containing a repeating unit represented by the formula (1), a binder resin, a photo acid generator (PAG) and the remaining solvent, If necessary, it may further contain a crosslinking agent and a silane compound.

Examples of the binder resin include novolac resin having a phenolic hydroxyl group, polyhydroxy styrene (polyvinylidene chloride), polyvinylidene chloride (PHS) resin, polyhydroxy styrene, and the like, represented by the following formula (4), and a leaving group Y which can be easily separated by an acid generated by the photoacid generator Is most preferred.

[Chemical Formula 4]

In the above formula (4), a and b are 0 to 100 mol%, preferably 0 to 50 mol% and 50 to 100 mol%, respectively, of the repeating units constituting the compound, 0 to 30 mol% and 70 to 100 mol%, respectively, the sum of a and b must be 100 mol%, and Y is the same as that described in the above formula (1).

The content of the binder resin is 1 to 100 parts by weight, preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by weight of the photosensitive polyimide resin, When the amount of the binder resin is less than 1 part by weight based on 100 parts by weight of the photosensitive polyimide resin, the improvement in resolution due to use of the binder resin may be small or may be insufficient. When the amount exceeds 100 parts by weight, And the physical properties of the film may not be satisfied. The weight average molecular weight (Mw) of the binder resin is 1,000 to 30,000, preferably 2,000 to 20,000, and more preferably 3,000 to 10,000.

The photoacid generator is used for the composition containing the photosensitive polyimide resin according to the present invention to act as a chemically amplified composition and effectively controls the acid diffusion length to improve the resolution of the pattern have. The photoacid generator may be a conventional photoacid generator without limitation, preferably an ionic photoacid generator such as a sulfonium salt or an iodonium salt, a sulfonyldiazomethane-based, N-sulfonyloxyimide-based, Phenate, nitrobenzyl sulfonate, sulfone, glyoxime, and triazine.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate (sulfonate anion), and the sulfonium cation is triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4-tert-butylphenyl) phenylsulfonium, 4-methylphenyldiphenylsulfonium, tris (4-methylphenylsulfonium) Tert-butoxyphenyl) sulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert- (3,4-di-tert-butoxyphenyl) diphenylsulfonium, bis (3,4-di-tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) Carbonylmethyloxyphenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4- Methyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, diphenylmethyl 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, and tribenzylsulfonium. Examples of the sulfonate include trifluoromethanesulfonate, trifluoromethanesulfonate, , Nonafluorobutane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pendafluorobenzene sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluoro Toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphorsulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, and methane sulfonate.

The iodonium salt is a salt of an iodonium cation and a sulfonate. Examples of the iodonium cation include diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyliodonium, 4-methoxyphenylphenyliodonium, and the like.

Examples of the sulfonyldiazomethane-based photoacid generators include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropoxylsulfonyl) diazomethane, bis Bis (phenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diazomethane, bis Bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and bis (2-naphthylsulfonyl) diazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiamine, 4-methylphenylsulfonyldiazomethane, And sulfonylcarbonyldiazomethane such as trimethoxycarbonyl-4-methylphenylsulfonyldiazomethane and the like.

Examples of the N-sulfonyloxyimide-based photoacid generator include succinic acid imide, naphthalene dicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicar Heptene-2,3-dicarboxylic acid imide, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluoro, heptadecafluoro, heptadecafluoro, Tetrafluorobutane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate, toluene sulfonate, benzene sulfoxide Naphthalene sulfonate, camphorsulfonate, octane sulfonate, and dodecylbenzene sulfonate. Butane sulfonate and methane sulfonate.

Examples of the benzoin sulphonate-based photoacid generators include benzoin tosylate, benzoin mesylate, and benzoinbutane sulfonate. Examples of the nitrobenzyl sulfonate photoacid generator include 2,4-dinitrobenzylsulfonate , 2-nitrobenzylsulfonate, 2,6-dinitrobenzylsulfonate, and compounds in which a nitro group of benzyl is substituted with a trifluoromethyl group. Examples of the sulfonic acid photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2- Propane, 2-methyl-2- (p-toluenesulfonyl) propionone, 2- (cyclohexylcarbonyl) ) -2- (p-toluenesulfonyl) propane and 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one.

Examples of the glyoxime-based photoacid generator include bis-o- (p-toluenesulfonyl) -? - dimethylglyoxime, bis-o- (p- toluenesulfonyl) (p-toluenesulfonyl) -2, 3-pentanedionylglyoxime, bis-o- (p-toluenesulfonyl) -? - dicyclohexylglyoxime, bis- (N-butanesulfonyl) -? - dimethylglyoxime, bis-o- (n-butanesulfonyl) -? - dimethylglyoxime, bis- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -? - dicyclohexylglyoxime, bis- (Methanesulfonyl) -? - dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -? - dimethylglyoxime, bis -o- (1,1,1-trifluoroethanesulfonyl) -? - dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis- Octylsulfonyl) -? - dimethylglyoxime, bis-o- ( (P-fluorobenzenesulfonyl) -? - dimethylglyoxime, bis-o-dimethylglyoxime, bis-o-dimethylglyoxime, bis- o- (p-tert-butylbenzenesulfonyl) -? - dimethylglyoxime, bis-o- (xylenesulfonyl) -a-dimethylglyoxime and bis- .

The content of the photo-acid generator is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the photosensitive polyimide resin and the binder resin, If the content of the photo-acid generator is less than 0.1 part by weight based on 100 parts by weight of the photosensitive polyimide resin and the binder resin, there is a fear that the developer is not developed by the developing solution. If the content is more than 20 parts by weight, outgassing ) Phenomenon and storage stability may be deteriorated.

Next, the solvent used in the present invention is to form a uniform pattern profile by improving the flatness of the composition comprising the photosensitive polyimide resin according to the present invention and preventing the occurrence of stains due to coating, , And can be used without limitation without changing the pattern. Examples thereof include N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3- Butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and mixtures thereof.

The crosslinking agent which can be further included as needed forms a crosslinked structure with the above-mentioned binder resin, and conventional crosslinking agents can be used without limitation, but it is preferable to use a crosslinking agent containing an alkoxymethyl group. It is more preferable to use a cross-linking agent having two or more alkoxymethyl groups in order to increase the cross-linking density. In order to further increase the cross-linking density and improve the chemical resistance, the alkoxymethyl group is substituted with 4 Most preferred is the use of crosslinking agents having at least one crosslinking agent. On the other hand, from the viewpoint of reducing unevenness in the pattern dimension after curing (curing), at least one crosslinking agent having 6 or more alkoxymethyl groups should be contained. The content of the crosslinking agent is 1 to 30 parts by weight, preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the photosensitive polyimide resin and the binder resin, When the content of the crosslinking agent is less than 1 part by weight based on 100 parts by weight of the photosensitive polyimide resin and the binder resin, there is a problem that a film having high chemical resistance can not be obtained. When the amount is more than 30 parts by weight, May be deteriorated.

The silane compound which can be further included as needed can improve the adhesion between the composition of the present invention and the substrate. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N Vinylnaphthyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (? -Methoxyethoxy) silane, 3- Methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and And mixtures thereof. When the silane compound is used in the composition according to the present invention, the amount of the silane compound used is 0.01 to 15 parts by weight, preferably 0.1 to 13 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the photosensitive polyimide resin and the binder resin Is 0.5 to 10 parts by weight. When the silane compound is used within the above range, the heat resistance of the photoresist composition containing the photosensitive polyimide resin according to the present invention can be maintained and sufficient effect as an adhesive can be obtained.

The method of forming a polymer film using a composition comprising a photosensitive polyimide resin according to the present invention includes a step of forming a film by applying a composition containing the photosensitive polyimide resin on a semiconductor substrate, , Developing with a developing solution to form a pattern, and curing to remove the solvent. Here, the polymer film can be used, for example, as a surface protective film of a semiconductor device, an interlayer insulating film, and an insulating layer of an organic electroluminescent device.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

[Preparation Example 1] Preparation of photosensitive polyimide resin

15 g (0.041 mol) of the diamine monomer represented by the above formula (2c) was dissolved in 109 g of N-methyl pyrrolidone (NMP) solvent under a dry nitrogen flow, and then the dianhydride monomer (Polyimide precursor), followed by the addition of 20 g of pyridine catalyst and 26 g of acetic anhydride (Ac ₂ O), followed by stirring for 6 hours at room temperature Followed by further stirring and reaction, to give an imidized (pre-imide cyclized) polyimide. Subsequently, 12.4 g of ethyl vinyl ether (EVE) and 18.79 g of para-toluene sulfonic acid (PTSA) were added to the imidized polyimide, and the mixture was stirred and reacted at a temperature of 60 ° C for 12 hours. , The reaction solution was added to 2 liters of water (H ₂ O) and filtered to produce a solid precipitate. Next, the precipitate was washed three times with a washing solution in which water and methanol were mixed at a ratio of 9: 1, and dried in a vacuum drier set at 60 ° C for 72 hours to obtain photosensitive polyimide (See above scheme 1). The molecular weight of the prepared photosensitive polyimide resin was measured by Gel Permeation Chromatography (GPC), and the relative imidization ratio was calculated by Fourier Transform-Infrared Spectroscopy (FT-IR) Was 16,000, and the imidization rate was 90%.

[Production Examples 2 to 14] Preparation of photosensitive polyimide resin

Each photosensitive polyimide resin was prepared in the same manner as in Preparation Example 1, except that the kind of diamine and dianhydride and the amount of other additives used were changed as shown in the composition of Table 1 below. , And the average molecular weight and the relative imidization rate of the photosensitive polyimide resin prepared above were shown.

Molecular Weight Imidization rate (%) Production Example 1 16,000 90 Production Example 2 18,000 89 Production Example 3 18,000 91 Production Example 4 24,000 90 Production Example 5 16,000 90 Production Example 6 16,500 89 Production Example 7 17,000 92 Production Example 8 17,000 90 Production Example 9 15,000 89 Production Example 10 16,000 90 Production Example 11 16,500 91 Production Example 12 20,000 92 Production Example 13 21,000 90 Production Example 14 20,000 92

[Preparation Example 15] Preparation of polyimide precursor

Polyamic acid as a polyimide precursor was prepared in the same manner as in Preparation Example 1, except that pyridine, acetic anhydride, ethyl vinyl ether and para-toluene sulfonic acid were not added as shown in Table 1 .

[Production Example 16] Preparation of binder resin

After dissolving 50 g of polyhydroxy styrene (PHS) having a molecular weight of 12,000 in 1 L of tetrahydrofuran (THF) solvent, 53.4 g of pyridine, 48.7 g of ethyl vinyl ether (EVE) and 128.4 g of para-toluenesulfonic acid (PTSA) was added, and the reaction was allowed to proceed at room temperature and in a dry nitrogen atmosphere for 24 hours. The reaction-terminated solution was gradually added dropwise to 5 L of heptane solvent to obtain a precipitated white powdery polymer, which was then washed with an excess amount of solvent and then dried in a vacuum drier set at 40 DEG C for 24 hours to obtain a binder resin .

[Example 1] Preparation of a composition comprising photosensitive polyimide resin

6.5 g of the photosensitive polyimide resin prepared in Preparation Example 1, 3.5 g of the binder resin prepared in Preparation Example 16 and 0.5 g of Irgacure PAG 103 (BASF Co., Germany) as a photo acid generator were mixed with 15 g of gamma butyrolactone , GBL) solvent to prepare a composition.

[Examples 2 to 14] Preparation of compositions containing photosensitive polyimide resin

A composition was prepared in the same manner as in Example 1, except that the types of the photosensitive polyimide resin were different, as shown in the composition of Table 3 below.

Polyimide resin Binder resin Photoacid generator
(Or photoactive compound) menstruum Example 1 Production Example 1 Production Example 16 PAG 103 GBL Example 2 Production Example 2 Production Example 16 PAG 103 GBL Example 3 Production Example 3 Production Example 16 PAG 103 GBL Example 4 Production Example 4 Production Example 16 PAG 103 GBL Example 5 Production Example 5 Production Example 16 PAG 103 GBL Example 6 Production Example 6 Production Example 16 PAG 103 GBL Example 7 Production Example 7 Production Example 16 PAG 103 GBL Example 8 Production Example 8 Production Example 16 PAG 103 GBL Example 9 Production Example 9 Production Example 16 PAG 103 GBL Example 10 Production Example 10 Production Example 16 PAG 103 GBL Example 11 Production Example 11 Production Example 16 PAG 103 GBL Example 12 Production Example 12 Production Example 16 PAG 103 GBL Example 13 Production Example 13 Production Example 16 PAG 103 GBL Example 14 Production Example 14 Production Example 16 PAG 103 GBL Comparative Example 1 Production Example 15 PHS PAC GBL

[Comparative Example 1] Preparation of a composition containing a polyimide precursor

As shown in Table 3, 6.5 g of the polyimide precursor (polyamic acid) prepared in Production Example 15, 3.5 g of polyhydroxystyrene (PHS, VP-8000, Nippon Soda Co., active compound, 2,3,4,4'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5 (2,3,4,4'-tetrahydroxybenzophenone-5 -sulfonate, diazonaphthoquinone ester compound, Toyo Gosei, Japan) was dissolved in 15 g of gamma-butyrolactone (GBL) solvent to prepare a composition.

[Examples 1 to 14, Comparative Example 1] Evaluation of pattern-formed films

The compositions prepared in Examples 1 to 14 and Comparative Example 1 were spin-coated on a silicon wafer using an ACT 8 track (Tokyo electron, Japan) and heated (baked) at a temperature of 120 ° C for 5 minutes A film having a thickness of 10 mu m was obtained. Subsequently, the film was exposed using a MA-6 mask aligner having a broadband wavelength and a mask having a pattern of 1 to 10 mu m L / S, and then developed with a TMAH developer (2.38 wt%) for 120 seconds, Sized pattern was obtained. The patterned film was cured at a temperature of 200 ° C for 60 minutes, immersed in N-methylpyrrolidone solvent at room temperature for 10 minutes, and washed with water to measure film thickness and resolution. Table 4 below shows the amount of energy exposed to the film, the change in film thickness (film residual film ratio), and resolution.

Exposure energy (mJ) Resolution (㎛) Film residual film ratio (%) Example 1 200 2 90 Example 2 350 2 95 Example 3 350 2 95 Example 4 350 2 95 Example 5 300 2 95 Example 6 250 2 90 Example 7 250 2 90 Example 8 250 2 90 Example 9 300 2 92 Example 10 350 2 92 Example 11 300 2 93 Example 12 350 2 93 Example 13 350 2 93 Example 14 350 2 92 Comparative Example 1 200 10 0

As shown in Table 4, the photosensitive polyimide resin and the binder resin used in the present invention are chemically amplified resist (CAR), in which an acetal group having a low activation energy is easily released (Comparative Example 1) using polyamic acid (polyimide precursor), which has been used in the past, has a film residual ratio of 0% when cured at a temperature of 200 ° C. Otherwise, it is possible to cure at a temperature of 200 ° C, and it can be seen that the film can be stably produced.

Claims (13)

1. A photosensitive polyimide resin comprising a repeating unit represented by the following formula (1).
[Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which can be bonded to an oxygen atom of a hydroxy group contained in X or R and can be separated by an acid and is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms, , b, c, and d are numbers of Y, and each is an integer of 0 to 4, and the sum of a, b, c, and d is 1 or more. The compound according to claim 1, wherein Y is a group selected from the group consisting of an acetal group, a ketal group, a carbonate group, and an ester group, which is bonded to an oxygen atom of a hydroxyl group contained in X or R in the formula (1) Photosensitive polyimide resin. The method of claim 1,

,

,

,

,

,

And

≪ / RTI > The photosensitive polyimide resin as claimed in claim 1, wherein the photosensitive polyimide resin represented by the formula (1) is obtained by reacting a diamine compound and a dianhydride compound, Wherein the photosensitive polyimide resin is produced by adding a compound containing a saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms. 5. The photosensitive polyimide resin according to claim 4, wherein the monomer of the diamine compound is represented by the following general formula (2a) to (2e), and the monomer of the dianhydride compound is represented by the following general formulas (3a) to (3e).
(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

The photosensitive polyimide resin according to claim 4, wherein the reaction is carried out at a temperature of -30 to 200 캜 for 2 to 24 hours. 1. A composition comprising a photosensitive polyimide resin comprising a repeating unit represented by the following formula (1), a binder resin, a photoacid generator, and the remaining solvent.
[Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which can be bonded to the oxygen atom of the hydroxy group contained in X or R and can be separated by an acid, is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms, and a, b, c and d are the numbers of Y, and each is an integer of 0 to 4, and the sum of a, b, c and d is 1 or more. [7] The composition according to claim 7, wherein the binder resin is represented by the following formula (4) and comprises a leaving group (Y) which can be easily separated by an acid generated by the photoacid generator .
[Chemical Formula 4]

Wherein a and b each represent 0 to 100 mol% of a and b each in terms of mol% of each repeating unit constituting the compound, the sum of a and b must be 100 mol% Is the same as that described in formula (1). [7] The photoacid generator according to claim 7, wherein the photoacid generator is at least one selected from the group consisting of a sulfonium salt, an ionic photoacid generator of an iodonium salt, a sulfonyldiazomethane-based, N-sulfonyloxyimide-based, benzoinisulfonate-based, nitrobenzylsulfonate- Wherein the photosensitive polyimide resin is selected from the group consisting of phthalic, glyoxime, and triazine. 8. The process of claim 7, wherein the solvent is selected from the group consisting of N-methyl-2-pyrrolidone, gamma -butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1 , 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and mixtures thereof. . The photosensitive resin composition according to claim 7, wherein the content of the binder resin is 1 to 100 parts by weight based on 100 parts by weight of the photosensitive polyimide resin, and the content of the photoacid generator is 100 parts by weight or less based on 100 parts by weight of the photosensitive polyimide resin and the binder resin. 0.1 to 20 parts by weight, and the balance being a solvent. [Claim 7] The composition according to claim 7, wherein the photosensitive polyimide resin has a weight average molecular weight of 1,000 to 200,000, and the binder resin has a weight average molecular weight of 1,000 to 30,000. Applying a composition comprising the photosensitive polyimide resin on a semiconductor substrate to form a film;
Exposing the film with an exposure mask and an exposure machine;
Developing with a developer to form a pattern; And
A curing step for removing the solvent,
Wherein the composition comprising the photosensitive polyimide resin comprises a photosensitive polyimide resin containing a repeating unit represented by the following formula (1), a binder resin, a photoacid generator, and the remaining solvent.
[Chemical Formula 1]

Wherein X and R are the same or different, X is an organic group containing an aromatic ring compound, R is an organic group containing no aromatic ring compound or an aromatic group containing no aromatic ring compound , Y is a leaving group which can be bonded to the oxygen atom of the hydroxy group contained in X or R and can be separated by an acid, is a hydrocarbon group having 1 to 20 carbon atoms and containing 1 to 10 oxygen atoms, and a, b, c and d are the numbers of Y, and each is an integer of 0 to 4, and the sum of a, b, c and d is 1 or more.