TW201922813A - Photosensitive polymer, photoresist composition using the same and pattern forming method useful in displays, semiconductors, and MEMS processes - Google Patents

Abstract

Disclosed are a photosensitive polymer used in displays, semiconductors, and MEMS processes, a photoresist composition using the photosensitive polymer, and a pattern forming method using the same. This invention provides a polymer comprising a repeat unit represented by chemical formula 1, a repeat unit represented by chemical formula 2, and a repeat unit represented by chemical formula 3. In chemical formulae 1 to 3, R1 individually represents hydrogen atom or methyl; R3 is a C1-C40 hydrocarbyl group and may contain at least one heteroatom selected from a group consisting of oxygen, sulfur and nitrogen; a, b and c are molar percentage of repeat unit constituting the polymer, wherein a is 5-30 mole%, b is 40-90 mole%, and c is 5-30 mole%.

Description

Photosensitive polymer, photoresist composition using the same, and pattern forming method

The present invention relates to a photosensitive polymer, a photoresist composition using the same, and a pattern forming method, and more particularly, to a photopolymer used in the production of a high-output powder light-emitting diode (LED) die for semiconductors, displays, and the like. Photosensitive polymer, photoresist composition using the same, and pattern forming method.

In display, semiconductor, and micro-electromechanical systems (MEMS) processes, lift-off PR is mainly used in the metal wiring evaporation process. According to the type and thickness of the metal wiring to be formed, a chemical vapor deposition (CVD) process and a metal vapor deposition using an electron beam (E-beam) are performed. In the metal evaporation process, the temperature will rise, and the process will usually be performed at about 100 ° C. However, in certain metal processes, the temperature will usually rise above 200 ° C.

If the heat resistance of the peeling photoresist (PR) used is insufficient, it is difficult to obtain a desired metal wiring due to pattern distortion at high temperatures. In addition, a stripping step is required to strip off unnecessary photoresist portions after the metal process, but it is difficult to remove it due to the high degree of crosslinking. Due to this problem, metal wiring that requires high heat resistance is usually manufactured by a dry etching process.

Therefore, an object of the present invention is to provide a photosensitive polymer having a high heat resistance of 200 ° C. or higher to facilitate a stripping step in order to obtain a desired metal wiring, and a photoresist composition using the photosensitive polymer. And a pattern forming method using the same.

Another object of the present invention is to provide a photosensitive polymer produced by a high-output powder light-emitting diode core by a simpler process than a conventional dry etching process, and a photoresist combination using the photosensitive polymer. Object and pattern forming method using the same.

In order to achieve the object, the present invention provides a polymer including a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the Chemical Formula 2 and a repeating unit represented by the Chemical Formula 3, [Chemical Formula 1] , [Chemical Formula 2] , [Chemical Formula 3]

In the chemical formula 1, chemical formula 2 and chemical formula 3, R ₁ is a hydrogen atom or a methyl group, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, and may include one or more members selected from the group consisting of oxygen, sulfur, and nitrogen. The heteroatoms in the group, a, b, c are the mole percentage of repeating units constituting the polymer, a is 5 mole% to 30 mole%, b is 40 mole% to 90 mole%, and c is 5 mole percent to 30 mole percent.

In addition, the present invention provides a photoresist composition including a polymer including a repeating unit represented by Chemical Formula 1 below, a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, and a solvent. In addition, the present invention provides a pattern forming method, which comprises: coating and drying a photoresist composition containing a polymer, a photoacid generator, a crosslinking agent, and a solvent on an upper portion of a substrate; In the step of forming a photoresist layer, the polymer includes repeating units respectively represented by the following Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3; and exposing the photoresist layer to radiation in a prescribed pattern. A step of developing down to form a photoresist pattern and exposing the substrate; a step of vaporizing a metal on the photoresist pattern and the exposed substrate; and removing the photoresist on which the metal is vapor-deposited Step of forming a metal pattern by an agent pattern.

The photosensitive polymer of the present invention, a photoresist composition using the photosensitive polymer, and a pattern forming method using the same have high heat resistance of 200 ° C. or higher, and adopt a photoresist that facilitates a stripping step. Agent composition to omit the existing dry etching, so that the required metal wiring can be obtained by a relatively simple process.

Hereinafter, the present invention will be described in more detail.

The photosensitive polymer of the present invention includes a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the Chemical Formula 2 and a repeating unit represented by the Chemical Formula 3 as a release polymer having a pattern formed by metal wiring vapor deposition. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]

In the chemical formula 1, chemical formula 2 and chemical formula 3, R ₁ is a hydrogen atom or a methyl group, respectively, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, preferably a hydrocarbon group having 1 to 35 carbon atoms, as required It may contain more than one heteroatom such as oxygen, sulfur, nitrogen, etc. For example, it may be a linear hydrocarbon group having a carbon number of 1 to 40 or a linear hydrocarbon group having a carbon number of 3 to 40 including a functional group including an ether group, a carbonyl group, an ester group, and a hydroxyl group. Cyclic hydrocarbon group. In addition, a, b, and c are the mole percentages of the repeating units constituting the polymer, a is from 5 moles to 30 moles, for example, a is from 10 moles to 20 moles, and b is 40 moles. Percent to 90 mole percentage, for example, b is 50 mole percentage to 80 mole percentage, c is 5 mole percentage to 30 mole percentage, for example, c is 10 mole percentage to 20 mole percentage.

In the repeating unit represented by the chemical formula 3, a specific example of a monomer including R ₃ may be (Chemical Formula 3a), (Chemical Formula 3b), (Chemical Formula 3c), (Chemical Formula 3d), (Chemical Formula 3e), (Chemical Formula 3f), (Chemical formula 3g), (Chemical formula 3h), (Chemical Formula 3i), (Chemical Formula 3j), (Chemical formula 3k), (Chemical formula 3l), (Chemical formula 3m), (Chemical Formula 3n) and the like, in the Chemical Formulas 3a to 3n, R ₁ is a hydrogen atom or a methyl group, respectively.

The photosensitive polymer may include a polymer represented by the following Chemical Formula 4. [Chemical Formula 4]

In the chemical formula 4, R ₁ is a hydrogen atom or a methyl group, respectively, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, preferably a hydrocarbon group having 1 to 35 carbon atoms, and may include more than one Heteroatoms such as oxygen, sulfur, and nitrogen may be, for example, linear hydrocarbon groups having 1 to 40 carbon atoms or cyclic hydrocarbon groups having 3 to 40 carbon atoms including functional groups such as ether groups, carbonyl groups, ester groups, and hydroxyl groups. In addition, a, b, and c are the mole percentages of the repeating units constituting the polymer, a is from 5 moles to 30 moles, for example, a is from 10 moles to 20 moles, and b is 40 moles. Percent to 90 mole percentage, for example, b is 50 mole percentage to 80 mole percentage, c is 5 mole percentage to 30 mole percentage, for example, c is 10 mole percentage to 20 mole percentage.

For the photosensitive polymer, when the repeating unit (repeating unit including a carboxylic acid) represented by Chemical Formula 1 is less than 5 mol%, there is a problem that it is difficult to peel off, and when it is greater than 30 mol% Next, there is a problem that a pattern cannot be obtained because the developing speed generated by the developing solution is too fast. When the repeating unit (repeating unit including a phenol unit) represented by Chemical Formula 2 is less than 40 mol%, there is a The problem is that the curing degree between the crosslinking agents becomes poor and the pattern cannot be obtained. When the percentage is greater than 90 mol, there is a problem that it cannot be peeled off because of the high curing degree with the crosslinking agent. When the content of the repeating unit (including the repeating unit of R ₃ ) is less than 5 mol%, there is a problem that the pattern is cracked when a thick pattern is formed. In the case of more than 30 mol%, there is a problem due to It is difficult for the developer to form swelling to achieve a desired pattern. The weight-average molecular weight of the photosensitive polymer is 1,000 to 100,000, and preferably 3,000 to 20,000. If the weight average molecular weight of the polymer is less than 1,000, a pattern cannot be formed due to a lack of a degree of crosslinking, and if it is greater than 100,000, it is difficult to achieve dissolution by a developer and peeling by a peeler.

The repeating unit represented by the chemical formula 1 can easily remove unnecessary photoresist by increasing the solubility by using a 2.38 wt% tetramethylammonium hydroxide (TMAH) developer and a striper, and thus can be obtained For the required metal wiring, the repeating unit represented by the chemical formula 2 can be combined with a cross-linking agent (X-linker) to increase the degree of cross-linking of the photoresist, and can include a hydroxyl group. The solubility produced by the stripper is further increased. The repeating unit represented by the chemical formula 3 achieves the effects of ensuring the physical properties such as preventing the occurrence of cracks in the film by adjusting the toughness of the photosensitive polymer and improving the solubility by the peeler. In addition, by applying the photosensitive polymer to a photoresist composition, the degree of effective cross-linking is increased, so that it does not occur at a temperature of 200 ° C. or higher, which is usually generated during metal evaporation. The pattern is deformed to ensure heat resistance.

The photosensitive polymer according to the present invention may be a block copolymer or a random copolymer, and the repeating unit represented by the chemical formula 1, chemical formula 2 and chemical formula 3 may be polymerized by a conventional method. For example, the monomers of the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2 and the repeating unit represented by the chemical formula 3 are simultaneously dissolved with the initiator and slowly dripped into the reactor containing the solvent in advance, By reacting for 24 hours from this, a random copolymer having a random structure of each repeating unit can be obtained. On the other hand, if a local monomer is reacted in advance to polymerize a low-molecular weight polymer and other monomers are sequentially polymerized, a block copolymer in which a plurality of blocks are linearly connected can be obtained.

The photoresist composition according to the present invention includes the photosensitive polymer and a solvent. The solvent can achieve the effect of forming a uniform pattern profile by achieving flatness of the photosensitive polymer and preventing the generation of coating spots. For example, the solvent is selected from the group consisting of N-methyl-2-pyrrolidone, γ- Butyrolactone, N, N-dimethylacetamidamine, dimethyl sulfene, diethylene glycol dimethyl ether, diethylene glycol diethanol ether, diethylene glycol dibutyl ether, propylene glycol methyl ether , Dipropylene glycol methyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butanediol acetate, 1,3-butanediol-3-mono It is composed of components in the group consisting of methyl ether, methylpyruvate, ethylpyruvate, methyl 3-methoxypropionate, and mixtures thereof. For the photoresist composition, the content of the solvent may be adjusted according to a thickness to be used, that is, a thickness formed by spin coating. Generally, for the photoresist composition, a thickness of 1 to 10 μm is formed by spin coating, and in this case, the amount of the solvent used is 100 to 900 parts by weight with respect to the solid content.

The photoresist composition according to the present invention may further include a crosslinking agent.

The cross-linking agent achieves a binding effect by forming a cross-linking structure with a photosensitive polymer, and preferably contains an alkoxymethyl group. The alkoxymethyl group usually forms a crosslinked bond at a temperature of 150 ° C. In order to increase the crosslinking density, a compound having two or more alkoxymethyl groups is preferred. In order to increase the heat resistance by increasing the density, A compound having four or more alkoxymethyl groups is preferred. And, in order to reduce the pattern size unevenness after elimination, it is preferable to include at least one compound having six or more alkoxymethyl groups. Preferably, the cross-linking agent like the alkoxymethyl group is contained in an amount of 1 to 30 parts by weight relative to 100 parts by weight of the photosensitive polymer, and more preferably, 1 to 20 parts by weight. When the content of the crosslinking agent is less than 1 part by weight, a pattern may not be obtained due to insufficient crosslinking degree, and when it is more than 30 parts by weight, peeling cannot be performed by a peeler.

The photoresist composition according to the present invention may further include a photoacid generator.

As long as it is a conventional photoacid generator for a photoresist composition, the use of the photoacid generator (PAG, Photo acid generator) is not particularly limited. As examples of the photoacid generator, ionic photoacid generators such as sulfonium salts and iodonium salts, and sulfonyldiazomethanes, N-sulfonyloxyimines, and benzoin are preferably used. Photoacid generators such as sulfonates, nitrobenzyl sulfonates, amidines, ethylenedioximes, and triazines.

Specifically, the sulfonium salt is composed of a salt of a sulfonium cation and a sulfonate (sulfonate anion). The sulfonium cation may be selected from triphenol hydrazone, (4-tert-butoxyphenyl) diphenylphosphonium, bis (4-tert-butoxyphenyl) phenylphosphonium, 4-methylphenyldiphenyl鋶, tris (4-methylphenyl 鋶), 4-tert-butylphenyldiphenyl 鋶, tris (4-tert-butylphenyl) 丁基, tris (4-tert-butoxyphenyl) 鋶, (3-tert-butoxyphenyl) diphenylphosphonium, bis (3-tert-butoxyphenyl) phenylphosphonium, tris (3-tert-butoxyphenyl) phosphonium, (3,4-di-tert-butyloxy) Butoxyphenyl) diphenylphosphonium, bis (3,4-di-tert-butoxyphenyl) phenylphosphonium, tri (3,4-di-tert-butoxyphenyl) fluorene, diphenyl (4 -Thiophenoxyphenyl) fluorene, (4-tert-butoxycarbonylmethoxyphenyl) diphenylphosphonium, tris (4-tert-butoxycarbonylmethoxyphenyl) phosphonium, (4-tert- Butoxyphenyl) bis (4-dimethylaminophenyl) fluorene, tris (4-dimethylaminophenyl) fluorene, 2-naphthyldiphenylfluorene, dimethyl-2-naphthyl Fluorene, 4-hydroxyphenyldimethylfluorene, 4-methoxyphenyldimethylfluorene, trimethylfluorene, diphenylmethylfluorene, methyl-2oxopropylphenylfluorene, 2- In the group consisting of oxocyclohexylcyclohexylmethylfluorene, trinaphthylfluorene, tribenzylfluorene, and mixtures thereof, The sulfonate (sulfonic anion) can be selected from trifluoromethanesulfonate, nonafluorobutanesulfonate, heptafluorooctanesulfonate, and 2,2,2-trifluoroethanesulfonate. , Pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate Acid salt, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and mixtures thereof.

The iodonium salt is a salt of an iodonium cation and a sulfonate (sulfonic anion), and the iodonium cation can be selected from diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4- In the group consisting of tert-butoxyphenylphenyliodonium, 4-methoxyphenylphenyliodonium, and mixtures thereof, the sulfonate can be selected from trifluoromethanesulfonate and nonafluorobutane Alkane sulfonate, heptafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene Sulfonate, tosylate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate or methanesulfonate, and In a group of their mixtures.

The sulfonyldiazomethane photoacid generator includes bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, and bis (2-methylpropylsulfonate). Fluorenyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (perfluoroisopropylsulfonyl) diamine N-methane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, Bis (2-naphthylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2- Naphthylsulfonylbenzyldiazomethane, 4-methylphenylsulfonyl-2-naphthylhydrazone diazomethane, methylsulfonylbenzyldiazomethane, or tert-butoxycarbonyl Disulfonyldiazomethane and sulfonylcarbonyldiazomethane such as 4-methylphenylsulfonyldiazomethane.

The N-sulfonyloxyimine photoacid generator may be selected from the group consisting of sulfonium imine succinate, fluorene imine naphthalene dicarboxylate, fluorene imine phthalate, fluorene imine cyclohexyl dicarboxylate, 5- Benzene imine skeletons such as norbornene-2,3-dicarboxylic acid imine or 7-heterobicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid imine And trifluoromethanesulfonate, nonafluorobutanesulfonate, heptafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoro Methylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, Butane sulfonate, methane sulfonate, and mixtures thereof.

The benzoin sulfonate-based photoacid generator may include benzoin tosylate, benzoin mesylate, benzoin butane sulfonate, and the like. The nitrobenzylsulfonate photoacid generator may be selected from 2,4-dinitrobenzylsulfonate, 2-nitrobenzylsulfonate, and 2,6-dinitrobenzylsulfonate. In the group consisting of acid salts and mixtures thereof, the sulfonate may be selected from trifluoromethanesulfonate, nonafluorobutanesulfonate, heptafluorooctanesulfonate, 2,2,2-tris Fluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate Acid salt, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, and mixtures thereof. In addition, a compound in which a nitro group on the benzyl side is substituted with a trifluoromethyl group may be included.

The fluorene type photoacid generator can be selected from bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2 -Bis (phenylsulfonyl) propane, 2,2-bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl- 2- (p-toluenesulfonyl) acetone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentane- 3-ketones and their mixtures.

The ethylenedioxime photoacid generator can be selected from bis-o-o- (p-toluenesulfonyl) -α-dimethylethylenedioxime and bis-o-o- (p-toluenesulfonyl) -α-dimethyl Ethylenedioxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylethylenedioxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedione ethylenedioxime, Bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione ethylenedioxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime , Bis-o- (n-butanesulfonyl) -α-dimethylethylenedioxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylethylenedioxime, bis-o-o- ( N-butanesulfonyl) -2,3-pentanedione ethylenedioxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedione ethylenedioxime, Bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,1 , 1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluoro Octanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexylsulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α- Dimethylglyoxime, bis-o-o- (pair Fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylylenesulfonyl) ) -α-dimethylglyoxime, bis-o- (camphorsulfonyl) -α-dimethylglyoxime, and mixtures thereof.

The content of the photoacid generator is 1 to 30 parts by weight, and preferably 1 to 10 parts by weight with respect to 100 parts by weight of the photosensitive polymer. When the content of the photoacid generator is less than 1 part by weight, there is a problem that it cannot be removed by a developing solution, and when it is more than 30 parts by weight, there is a problem that outgassing and storage stability are reduced. .

In addition, in order to improve adhesion to the base substrate, the photoresist composition of the present invention may further include a silane compound. Specific examples of the silane compound that can be contained in the composition include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N -Phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethylene Trichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acrylateoxypropyltrimethoxysilane, p-styryl Trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, or a silane compound having a structure shown below, and The group consisting of a combination of two or more of them is not limited thereto. Preferably, the content of the silane compound is 0.01 to 15 parts by weight relative to 100 parts by weight of the total amount of the photoresist composition. If it is in the said range, the adhesive effect can fully be acquired, maintaining the heat resistance of a photoresist composition.

The pattern forming method of the present invention includes forming a photoresist by coating the photoresist composition of the present invention on an upper portion of a substrate (for example, a sapphire or silicon wafer having a GaN or ITO layer formed thereon) and drying the photoresist composition. A step of forming a photoresist layer; a step of exposing the photoresist layer under radiation in a prescribed pattern and developing to form a photoresist pattern and exposing a substrate; and in the photoresist A pattern and a step of vaporizing metal on the exposed substrate; and a step of removing a photoresist pattern on which the metal is vapor-deposited to form a metal wiring.

Specifically, a composition containing the photosensitive polymer, a photoacid generator, a cross-linking agent, and a solvent is applied on the substrate to form a photoresist layer. Selective exposure with a desired pattern mask on the formed photoresist layer can be performed by using a conventional alkaline aqueous solution such as a tetramethylammonium hydroxide developer (developer). Develop to remove unnecessary photoresist. A metal is vapor-deposited by an exfoliation process on the upper part of the photoresist layer and the upper part of the substrate. In this case, the temperature is generally raised to 200 ° C. or higher during the metal evaporation process, and the photoresist composition can also be subjected to metal evaporation at high temperatures without causing pattern distortion. In order to peel off unnecessary photoresist layers other than the metal on the upper part of the substrate, a stripper will be used for removal. The said composition can improve the solubility with a peeler, and can peel easily the photoresist layer which vapor-deposited the said metal. Conventionally, the stripper has low solubility and poor heat resistance during metal deposition. Therefore, metal wiring can be obtained by a dry etching process due to problems such as pattern distortion. However, according to the present invention, the temperature is generally 200 ° C. The above high heat resistance and the peeling process can be easily realized, so that the required metal wiring can be obtained even when the conventional dry etching process is omitted. And, the photoresist composition according to the present invention can be used as a negative photoresist composition.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

[Examples 1-1 to 1-28] Polymer Synthesis

After 111 g of methanol (MeOH) was charged into the dual reactor (1 L), a circulation device was installed, and the temperature was raised to 70 ° C by a warm water circulation method and maintained. In other beakers, the monomers of the components and contents in Table 1 below were dissolved together with 6.26 g of the initiator V601, and slowly dripped into a dual reactor prepared in advance for 3 hours, and a reaction was performed for 24 hours. (Each Example 1-1 to Example 1-28). When the reaction is completed, the reaction solution is cooled to normal temperature, and after the precipitate and the reaction solution are separated, the reaction solution is removed. After adding 133.3 g of tetrahydrofuran (THF, 66.65 g) of methanol to the obtained precipitate, the temperature was raised to 50 ° C. by a warm water circulation method. In order to perform hydrolysis, 35.58 g of ammonia water was slowly added, and a reaction was performed for 12 hours. After the hydrolysis is completed, for neutralization, 24.17 g of acetic acid is slowly added, and then cooled to normal temperature. The solid content was precipitated and separated using pure water equivalent to 10 times the total amount of the reaction solution. The solid component obtained as described above was dried for 48 hours using a vacuum drying device at a temperature of 400 ° C to synthesize the photosensitive polymer (polymer for peeling) of the present invention (Example 1). -1 to Example 1-28). The molecular weight and dispersion of the synthesized release polymer were measured by a gel permeation chromatography (GPC) analyzer. Table 1 also shows the measurement results.

Table 1

MAA: Methylacrylic acid ACS: 4-acetoxy styrelne

[Example 2-1 to Example 2-24, Comparative Example 1 to Comparative Example 8] Preparation and evaluation of negative photoresist composition

The polymers obtained in Examples 1-1 to 1-28 and the photoacid generators of Heraeus (Germany), NIT (cas: 85342-62-7), and three were used. And chemical (SANWA CHEMICAL, Japan) MW-390 cross-linking agent. The solvent propylene glycol methyl ether acetate (PGMEA) was used to prepare a solid content of 30% according to each composition of Examples 2-1 to 2-25, and then filtered using a 0.45µm disc filter using TEL. The company's Mark-7 equipment coats silicon wafers at a thickness of 5.0 µm. In this case, the bake condition is 110 degrees / 60sec. A Nikon i9C device (0.57NA, conventional) was used to implement a 3.0µm trench pattern. A 2.38wt% tetramethylammonium hydroxide developer solution was used in a puddle method for 6.0 seconds. Clock (sec). In order to ensure heat resistance, the elimination was performed at 200 ° C for 4 hours using a convection oven. In order to determine whether there is deformation, the elimination was compared and measured using a Hitachi scanning electron microscope (Hitachi SEM, S4800). The cross sections before and after were evaluated for peeling using a stripper DPS-7300 (Dongjin Semiconductor) at a temperature of 60 ° C for 10 minutes under ultrasonic (200w / 36.6KHz) conditions, and shown in Table 2 below.

In Comparative Example 1, VP2500 (Nippon soda, Japan) synthesized by a polymer anion polymerization method was used. In Comparative Examples 2 to 8, the polymers in Table 2 below were used. All evaluations of Examples 2-1 to 2-24 and Comparative Examples 1 to 8 were performed under the same conditions.

Table 2

From the results shown in Table 2, the conventional PHS type polymer used in the comparative example can show excellent results in terms of heat resistance, but it is not good for use in the peeling step. According to the analysis of the examples, the polymer according to the present invention does not deform during a process at a temperature of 200 ° C. or higher, and can be easily peeled by a peeler.

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Claims (15)

A polymer including a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the Chemical Formula 2 and a repeating unit represented by the Chemical Formula 3: [Chemical Formula 1] , [Chemical Formula 2] , [Chemical Formula 3] In Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, R ₁ is a hydrogen atom or a methyl group, respectively, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, and may include one or more members selected from the group consisting of oxygen, sulfur, and nitrogen. The heteroatoms in the group, a, b, c are the mole percentages of the repeating units constituting the polymer, a is 5 mole% to 30 mole%, b is 40 mole% to 90 mole%, and c is 5 mole percent to 30 mole percent. The polymer according to item 1 of the scope of patent application, wherein the polymer including the repeating unit represented by the chemical formula 1, the repeating unit represented by the chemical formula 2 and the repeating unit represented by the chemical formula 3 includes the following chemical formula 4: [Chemical Formula 4] In Chemical Formula 4, R ₁ is a hydrogen atom or a methyl group, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, and may include one or more hetero atoms in a group consisting of oxygen, sulfur, and nitrogen. a, b, and c are the mole percentages of the repeating units constituting the polymer, a is from 5 moles to 30 moles, b is 40 to 90 moles, and c is 5 to 30 moles Ear percentage. The polymer according to item 1 of the patent application scope, wherein R ₃ is a linear hydrocarbon group or carbon having a carbon number of 1 to 40 containing a functional group selected from the group consisting of an ether group, a carbonyl group, an ester group, and a hydroxyl group The number is 3 to 40 cyclic hydrocarbon groups. The polymer according to item 1 of the scope of patent application, wherein the chemical formula 3 containing R ₃ is selected from a repeating unit in the group represented by the following chemical formulas 3a to 3n: (Chemical Formula 3a), (Chemical Formula 3b), (Chemical Formula 3c), (Chemical Formula 3d), (Chemical Formula 3e), (Chemical Formula 3f), (Chemical formula 3g), (Chemical formula 3h), (Chemical Formula 3i), (Chemical Formula 3j), (Chemical formula 3k), (Chemical formula 3l), (Chemical formula 3m), (Chemical Formula 3n) In Chemical Formula 3a to Chemical Formula 3n, R ₁ is a hydrogen atom or a methyl group, respectively. The polymer according to item 1 of the scope of patent application, wherein the polymer has a weight average molecular weight of 1,000 to 100,000. The polymer according to item 1 of the scope of patent application, wherein the polymer is a block copolymer or a random copolymer. A photoresist composition includes a polymer and a solvent, and the polymer includes a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the Chemical Formula 2 and a repeating unit represented by the Chemical Formula 3: [Chemical Formula 1] , [Chemical Formula 2] , [Chemical Formula 3] In Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, R ₁ is a hydrogen atom or a methyl group, respectively, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, and may include one or more members selected from the group consisting of oxygen, sulfur, and nitrogen. The heteroatoms in the group, a, b, c are the mole percentages of the repeating units constituting the polymer, a is 5 mole% to 30 mole%, b is 40 mole% to 90 mole%, and c is 5 mole percent to 30 mole percent. The photoresist composition according to item 7 of the patent application scope, further comprising a crosslinking agent. The photoresist composition according to item 8 of the patent application scope, wherein the crosslinking agent is a compound containing an alkoxymethyl group. The photoresist composition according to item 7 of the patent application scope further comprises a photoacid generator. The photoresist composition according to item 10 of the scope of patent application, wherein the photoacid generator is 1 to 30 parts by weight relative to 100 parts by weight of the polymer. The photoresist composition according to item 8 of the scope of patent application, wherein the crosslinking agent is 1 to 30 parts by weight relative to 100 parts by weight of the polymer. The photoresist composition according to item 7 of the scope of patent application, wherein the polymer further contains 0.01 to 15 parts by weight of a silane compound relative to 100 parts by weight of the polymer. The photoresist composition according to item 7 of the scope of application for a patent can be used as a negative photoresist composition. A pattern forming method includes the steps of forming a photoresist layer by coating a photoresist composition containing a polymer, a photoacid generator, a crosslinking agent, and a solvent on an upper portion of a substrate and drying the photoresist composition. The polymer includes a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the Chemical Formula 2 and a repeating unit represented by the Chemical Formula 3: [Chemical Formula 1] , [Chemical Formula 2] , [Chemical Formula 3] In Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3, R ₁ is a hydrogen atom or a methyl group, respectively, and R ₃ is a hydrocarbon group having 1 to 40 carbon atoms, and may include one or more members selected from the group consisting of oxygen, sulfur, and nitrogen. The heteroatoms in the group, a, b, c are the mole percentages of the repeating units constituting the polymer, a is 5 mole% to 30 mole%, b is 40 mole% to 90 mole%, and c is 5 Molar percentage to 30 Molar percentage; a step of exposing the photoresist layer to radiation to form a photoresist pattern and exposing the substrate in a prescribed pattern; the photoresist pattern and the A step of vaporizing a metal on the exposed substrate; and a step of removing the photoresist pattern on which the metal is vapor-deposited to form a metal wiring.