KR20080022347A - Chemically amplified positive photoresist composition - Google Patents

Abstract

A chemically amplified positive photoresist composition is provided to increase the light transmission by using an additive capable of inhibiting readsorption of a hydrophobic resin onto a wafer, to realize high sensitivity and resolution, and to form a high-quality pattern. A chemically amplified positive photoresist composition comprises: (A) a resin that is insoluble or hardly soluble in an aqueous alkali solution in nature but becomes soluble in an aqueous alkali solution after acid-liable microfibers are dissociated under the action of an acid; (B) a compound generating an acid under the action of light or radiation; and (C) a compound represented by the following formula 3. In formula 3, each of R7 and R8 represents a bond, a halogen-substituted or non-substituted C1-C6 linear or branched alkylene, or a halogen-substituted or non-substituted C2-C6 alkenylene, wherein the compound represented by formula 3 has a molecular weight of 100-1000.

Description

Chemically Amplified Positive Photoresist Composition

FIELD OF THE INVENTION The present invention relates to chemically amplified positive photoresist compositions suitable for photolithography or the like acting by ultraviolet radiation, such as excimer lasers, electron beams, X-rays or high energy radiation such as radiant light.

In recent years, as the degree of integration of integrated circuits has increased, submicron pattern formation has been required. In particular, photolithography using an excimer laser from fluoride krypton (KrF) or argon fluoride (ArF) has been noted in that it enables the production of 64M DRAM to 1G DRAM. As a resist suitable for a photolithography process using such an excimer laser, a so-called chemically amplified resist using an acid catalyst and a chemical amplification effect is adopted. When a chemically amplified resist is used, the acid generated from the photoacid generator is diffused by the subsequent heat treatment in the radiation irradiation unit, and the solubility in the alkaline developer of the irradiation unit is changed by the reaction using the diffused acid as a catalyst. Or a negative type pattern is obtained.

Chemically amplified positive type resists, particularly positive type resists for KrF excimer laser photolithography, are poly (hydroxystyrene) resins in which some of their phenolic hydroxyl groups are dissociated by the action of acid. It is often used in combination with a photoacid generator. A group that is dissociated by the action of such an acid, and forms an acetal bond between oxygen atoms derived from phenolic hydroxyl groups from the viewpoint of resolution and sensitivity, for example, tetrahydro-2-pyranyl Attention is drawn to resins in which tetrahydro-2-furyl or 1-ethoxyethyl are bonded to an oxygen atom. However, even when such a resin is used, there is a limit in the profile because the film is formed in a condition in which the film thickness is thick and the substrate has a specificity when used for the metal process and the implanter process.

In addition, when the film thickness is large and the exposure area is large and the volume of the resist that is soluble and removed in the aqueous alkali solution is high, the hydrophobic resins agglomerate and grow into particles in a hydrophilic atmosphere during ultrapure water cleaning. Therefore, the particles are resorbed to the part where the substrate is exposed by exposure and development, and the transmittance of the resist is reduced in the metal wiring or implant process, resulting in a profile in which the sensitivity, low resolution, and inclination are generated.

Thus, the present inventors while studying a chemically amplified positive photoresist composition that improves various performances such as sensitivity, resolution, etc. in order to overcome the above problems, a dihydroxy group having a molecular weight of 100 ~ 1000 and a hydrophilic group in cyclohexane The photoresist composition including the additive having the additive inhibits the resorption of the hydrophobic resin to the substrate in the semiconductor photo process to increase the transmittance, thereby confirming that the profile exhibits high sensitivity and high resolution and forms a profile free from development defects. It was.

The present invention seeks to provide a chemically amplified positive photoresist composition.

The present invention

(A) A resin which is originally insoluble or poorly soluble in aqueous alkali solution, but becomes soluble in aqueous alkali solution after dissociation of a functional group unstable with acid by the action of acid;

(B) a compound that generates an acid by the action of light or radiation, and

(C) Provides a chemically amplified positive photoresist composition comprising a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R ₇ and R ₈ are each independently a bond; C1-C6 linear or branched alkylene group in which a halogen atom is substituted or unsubstituted; Or a halogen atom is a substituted or unsubstituted C2-C6 alkenylene group, and molecular weight is 100-1000.

Hereinafter, the present invention will be described in detail.

Component (A) included in the chemically amplified positive photoresist composition of the present invention is insoluble or poorly soluble in aqueous alkali solution, but is soluble in aqueous alkali solution after dissociation of a functional group unstable with acid by the action of acid. It is resin which becomes. Examples of such a resin are resins obtained by introducing a protecting group that can be dissociated by the action of an acid into a resin soluble to an aqueous alkali solution, and for example, a resin having a hydroxystyrene skeleton in which a part of the hydroxy group is protected with a protecting group; And / or a resin having a (meth) acrylate skeleton in which a hydroxy group is protected by a protecting group.

Examples of protecting groups include groups in which quaternary carbons are bonded to oxygen atoms, such as t-butyl, t-butoxycarbonyl or t-butoxycarbonylmethyl; Tetrahydro-2-pyranyl, tetrahydro-2-furyl, 1-ethoxyethyl, 1- (2-methylpropoxy) ethyl, 1- (2-methoxyethoxy) ethyl, 1- (2-acetyl Acetal groups such as oxyethoxy) ethyl, 1- [2- (1-adamantyloxy) ethyl] ethyl or 1- [2- (1-adamantanecarbonyloxy) ethoxy] ethyl; And ratios such as 3-oxocyclohexyl, 4-methyltetrahydro-2-pyron-4-yl (derived from mevalonic acid lactone), 2-methyl-2-adamantyl or 2-ethyl-2-adamantyl Aromatic cyclic compounds. Among them, 1-ethoxyethyl group is particularly preferred because of its high stability against delay after exposure.

Therefore, in the present invention, as a resin component, it has a structure formed by partially protecting the hydroxyl group of hydroxystyrene with 1-ethoxyethyl group and partially formed by protecting the carboxyl group of (meth) acrylate with an alkyl group. Resin containing a polymerized unit having a structure is preferable.

As a method for producing the resin, a protecting group can be introduced into a alkali-soluble resin having a phenolic hydroxyl group or a carboxyl group by a known protecting group introduction reaction. In addition, the said resin can also be obtained by copolymerizing using an unsaturated compound which has such a group as one monomer.

In this invention, the polymer which has a repeating unit represented by following General formula (1) is preferable.

[Formula 1]

In Chemical Formula 1,

R ₁ is hydrogen or a methyl group,

R ₂ is hydrogen, a straight or branched chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms,

R ₃ and R ₄ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms,

a, b and c are the mole fractions of each monomer 0 to 1, respectively, a + b + c = 1, and 0.1≤ [(a + c) / (a + b + c)] ≤0.5 or 0.1≤ [c / (a + b + c)] ≤0.5 to be. On the other hand, [(a + c) / (a + b + c)] x 100 is a protection rate of the resin is preferably 10% to 50% of the resin.

Preferably, in Formula 1, a, b, and c are 0.20≤ [(a + c) / (a + b + c)] ≤0.40 or 0.1≤ [c / (a + b + c)] ≤0.20 Has a value. If the value of (a + c) / (a + b + c) or c / (a + b + c) is less than 0.10, all of the films are dissolved after development. Does not dissolve In addition, when c / (a + b + c) is more than 0.50, the dissolution rate in the developer is lowered and the contrast tends to be deteriorated.

(B) A compound which generates an acid by the action of light or radiation included in the chemically amplified positive photoresist composition of the present invention is a photoacid generator, and the material itself or a resist composition containing such a substance is ultraviolet, ultraviolet, or electron beam. It is a substance that generates acid by irradiating high energy radiation such as X-rays, or radiated light. The acid generated from the photoacid generator acts on the resin to dissociate the functional group that is unstable to the acid present in the resin.

In this invention, it is preferable to use the compound represented by following formula (2) as a photo-acid generator component.

[Formula 2]

In Formula 2, R ₅ and R ₆ are each independently a hydroxy group, an amino group or a C 1-10 straight or branched chain alkyl group unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms unsubstituted or substituted with a hydroxy group, an amino group or an alkoxy group having 1 to 6 carbon atoms; Or an alkyl group having 1 to 20 carbon atoms, alkoxy having 1 to 6 carbon atoms or an aryl group having 6 to 11 carbon atoms substituted or unsubstituted.

Preferably, in Formula 2, R ₅ and R ₆ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6- Triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group or benzyl group.

In addition, in the chemically amplified positive photoresist composition of the present invention, a photoacid generator other than the photoacid generator of Formula 2 may be used together. Such other photoacid generators include onium salt compounds, s-triazine-based organic halogen compounds, sulfone compounds, sulfonate compounds and the like. Specifically, the following compounds are listed:

Diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) Iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) Iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methylphenyldiphenylsulfonium perfluoro Butanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium triple Oromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium Hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphtolylmethyl) thi Olanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 2-methyl -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3-5-triazine, 2- (4 -Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] dioxolane-5 -Yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxy Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly referred to as' benzoin tosylate '), 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (usually' α- Methylolbenzoin tosylate '), 1,2,3-benzenetolyl Trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate, diphenyl disulfone, di-p-tolyl disulfone , Dis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazo Methane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, N- (phenylsulfonyloxy) succinate Mead, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene -2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsulfonyloxy) naphthalimide, 4-methoxy-α-[[ [(4-methylphenyl) sulfonyl] oxy] imino] benzeneacetonitrile, etc. It is included.

The content of the component (B) in the chemically amplified positive photoresist composition of the present invention preferably contains 0.1 to 20 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. If the content of the photoacid generator is less than 0.1 part by weight, a poor appearance appears at a resolution such as a development defect, and if it exceeds 20 parts by weight, the pattern shape is collapsed to hardly form a patterned resist layer.

The component (C) included in the chemically amplified positive photoresist composition of the present invention is soluble in an aqueous alkali solution by an acid generated from a photoacid generator at an exposure site during a semiconductor photo process, and the resin to be removed is poorly soluble. It serves to prevent becoming.

The resin, which was poorly soluble in the alkaline aqueous solution in the semiconductor photo process, is changed to soluble by an acid generated from a photoacid generator and is dissolved by receiving light, and fine patterns are realized by washing with ultrapure water. In this process, when the area of the exposed area is large, when the resin dissolved in the aqueous alkali solution is dissolved in ultrapure water, the resin becomes poorly soluble due to the high hydrophobicity of the resin and is resorbed to the substrate to form particles, thereby developing defects. Will occur. At this time, the component (C) is uniformly distributed between the resins to dilute the concentration of the resin to increase the transmittance, thereby preventing the hydrophobic resin from agglomerating again on the substrate during the ultrapure water cleaning process, thereby making it difficult to dissolve. Will inhibit adsorption. Therefore, it is possible to form a profile exhibiting high sensitivity and high resolution and without developing defects.

(C) component in the composition of this invention uses the compound represented by following formula (3).

[Formula 3]

In Formula 3, R ₇ and R ₈ are each independently a bond; C1-C6 linear or branched alkylene group in which a halogen atom is substituted or unsubstituted; Or a halogen atom is a substituted or unsubstituted C2-C6 alkenylene group, and molecular weight is 100-1000.

R ₇ and R ₈ are preferably a bond or di (trifluoromethyl) methylene, respectively .

The content of the component (C) in the chemically amplified positive photoresist composition of the present invention is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. If the content of the component (C) is less than 0.1 part by weight, the hydrophobic resin may not be resorbed to the substrate to improve development defects. If the content is more than 30 parts by weight, the weight ratio of the component (C) may be too large to increase resolution. There is a problem of deterioration.

The photoresist composition of the present invention may contain other organic base compounds, especially nitrogen-containing basic organic compounds as quenchers in amounts that do not adversely affect the effects of the present invention.

Specific examples of the nitrogen-containing basic organic compound include a compound represented by the following structural formula.

In the above structural formula, R ₉ and R ₁₀ are each independently hydrogen; C1-C6 linear or branched alkyl group substituted or unsubstituted by the hydroxyl group, the amino group, the C1-C4 alkyl group, or the C1-C6 alkoxy group; A C5-10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; Or an amino group substituted with a hydroxy group, an amino group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms,

R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen; C1-C6 linear or branched alkyl group substituted or unsubstituted by the hydroxyl group, the amino group, the C1-C4 alkyl group, or the C1-C6 alkoxy group; A C5-10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; A C1-6 alkoxy group unsubstituted or substituted with a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; Or an amino group substituted with a hydroxy group, an amino group, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms,

R ₁₄ is a hydroxy group, an amino group, an amino group substituted with an alkyl group having 1 to 4 carbon atoms, or a straight or branched chain alkyl group having 1 to 6 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; Or an amino group substituted with a hydroxy group, an amino group, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms,

A is a C2-C6 linear or branched alkylene group, carbonyl group, sulfide group, or disulfide group.

In addition, a hindered amine compound having a piperidine skeleton as described in Japanese Patent Laid-Open No. 11-52575 can be further used as a quencher.

In the resist composition of the present invention, the quencher preferably contains 0.001 to 10 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. If the content of the quencher is less than 0.001 parts by weight, the diffusion of acid is increased so that an abnormality in the exposed area is developed, and thus the pattern profile is deteriorated. By causing a change in the profile accordingly, the photosensitivity of the photoresist composition is rather reduced.

In addition, the chemically amplified positive photoresist compositions of the present invention may further contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes, and the like.

The chemically amplified positive photoresist composition is in the form of a resist liquid composition containing components dissolved in a conventional solvent, and is applied onto a substrate such as a silicon wafer by a conventional method. The solvent used in the present invention preferably dissolves the components, exhibits a suitable drying rate, and provides a uniform and smooth film after solvent evaporation, and those conventionally used in this field can be used. Examples thereof include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; Esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone; cyclic esters such as γ-butyrolactone; Alcohols such as 3-methoxy-1-butanol and the like. These solvents may each be used alone or as a mixture of two or more.

Using the chemically amplified positive photoresist composition according to the present invention, a resist pattern can be formed by the following method.

The chemically amplified positive photoresist composition according to the present invention is applied to an etched layer such as a silicon wafer or a chromium substrate by using a spin coater to form a thin film. An electron beam is injected into an exposure source to the formed thin film, and then the exposed resist film is heated as necessary to promote the protecting group removal reaction. The heated resist film is developed with an alkaline developer to form a resist pattern. Alkali developers used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide And various aqueous alkali solutions such as (2-hydroxyethyl) trimethylammonium hydroxide, among which tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (usually choline Is referred to).

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.

Example  1 to 4, and Comparative Example  1 to 4  :

According to the photoacid generator (4 parts by weight) based on 100 parts by weight (in terms of solids) of the resin component mixed in the ratio (in terms of solids) shown in Table 1, and according to the content and type shown in Table 1. The ammonium salt as quencher was dissolved in 370 parts by weight of propylene glycol monomethyl ether acetate and then filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist solution. The prepared resist solution includes a resin containing a degree of protection of 33% to 38%.

When the resist solution prepared above was applied to a silicon wafer treated with hexamethyldisilazane using a spin coater, the film thickness after drying was 1.208 µm. After applying the resist solution, preheat treatment was performed for 60 seconds on a hot plate at 100 ° C. The wafer having the resist film thus formed was gradually exposed to light using a scanning exposure apparatus ['NSR-S203B' manufactured by Nikon Corp., NA = 0.68, sigma == 0.75], having an exposure wavelength of 248 nm (KrF). Exposure was performed to form line and space patterns. Subsequently, in the hot plate, post-exposure heat treatment was performed at 110 ° C. for 60 seconds. In addition, paddle development was performed for 60 seconds using an aqueous 2.38% tetramethylammonium hydroxide solution. The developing defect was measured in the square space pattern of 50 micrometers using the KLA scanning electron microscope for the pattern after image development. In addition, the depth of focus and the profile were measured in a 0.4 μm line and space pattern.

The results are shown in Table 2.

A-1: Resin having a molecular weight of 20,000 and a degree of dispersion of 1.7 containing a cyclohexyl group protecting group with respect to a hydroxy group of hydroxystyrene and a carboxyl group of ethoxyethyl group / methacrylate, a = 0.23, c = 0.12.

(R ₁ : methyl group, R ₂ : methyl group, R ₃ : ethyl group, R ₄ : cyclohexyl group),

A-2: a resin having a molecular weight of 10,000, and polydispersity of 1.2 containing the ethoxyethyl protecting group for the hydroxyl group of hydroxystyrene a = 0.34, c = 0 ( R 2: methyl group, R _3: an ethyl group).

B-1: Diazodisulfone type photoacid generator in which R ₅ and R ₆ in Formula 2 are each cyclohexyl group,

C-1: 1,4-cyclohexanediol,

C-2: 1,2-cyclohexanediol,

C-3: In the formula (3), R ₇ and R ₈ are each di (trifluoromethyl) methylene,

C-4: polypropylene glycol (molecular weight 1000),

C-5: cresol,

C-6: 1,4-diisopropylcyclohexane

D-1: dicyclohexylmethylamine,

TABLE 1

Resin (part by weight) Photoacid Generator (parts by weight) Additive (part by weight) quencher Example 1 A-2 (100) B-1 (3.5) C-1 (2.1) D-1 (0.3) Example 2 A-1 (100) B-1 (3.5) C-1 (2.1) D-1 (0.2) Example 3 A-1 (100) B-1 (3.5) C-2 (2.1) D-1 (0.2) Example 4 A-2 (100) B-1 (3.5) C-3 (2.1) D-1 (0.3) Comparative Example 1 A-1 (100) B-1 (3.5) × D-1 (0.2) Comparative Example 2 A-1 (100) B-1 (3.5) C-4 (2.1) D-1 (0.2) Comparative Example 3 A-2 (100) B-1 (3.5) C-5 (2.1) D-1 (0.3) Comparative Example 4 A-2 (100) B-1 (3.5) C-6 (2.1) D-1 (0.3)

TABLE 2

profile Phenomenon defects Sensitivity (mJ / ㎠) q Example 1 ◎ 32 36 Example 2 ◎ 48 44 Example 3 ◎ 76 45 Example 4 ○ 69 46 Comparative Example 1 ○ 11,538 42 Comparative Example 2 ○ 10,268 42 Comparative Example 3 × 28,468 68 Comparative Example 4 × 27,606 42

As shown in Table 2, the chemically amplified positive photoresist composition (Examples 1 to 4) according to the present invention includes a cyclohexane having a molecular weight of 100 to 1000 as an additive having a dihydroxy group as a hydrophilic group, thereby improving the profile and sensitivity. It can be seen that it is excellent and no development defects appear.

On the other hand, the photoresist composition (Comparative Examples 1 to 4) containing no additive having a dihydroxy group which is a hydrophilic group in cyclohexane or including an additive of another structure showed a lot of development defects, so that the profile was badly formed.

The chemically amplified positive photoresist composition according to the present invention comprises an additive having a dihydroxy group which is a hydrophilic group in cyclohexane having a molecular weight of 100 to 1000, and is uniformly distributed between the resins in the semiconductor photo process to dilute the concentration of the resin to reduce the transmittance. Rising to prevent the re-adsorption of the hydrophobic resin on the substrate during the ultrapure water cleaning process. Therefore, it is possible to form a profile exhibiting high sensitivity and high resolution and without developing defects.

Claims (10)

(A) A resin which is originally insoluble or poorly soluble in aqueous alkali solution, but is soluble in aqueous alkali solution after dissociation of the microfine fiber which is unstable to acid by the action of acid, (B) a compound that generates an acid by the action of light or radiation, and (C) A chemically amplified positive photoresist composition comprising a compound represented by the following formula (3). [Formula 3]

In Formula 3, R ₇ and R ₈ are each independently a bond; C1-C6 linear or branched alkylene group in which a halogen atom is substituted or unsubstituted; Or a halogen atom is a substituted or unsubstituted C2-C6 alkenylene group, and molecular weight is 100-1000. The chemically amplified positive photoresist composition according to claim 1, wherein the resin (A) is a polymer having a repeating unit represented by the following formula (1). [Formula 1]

In Chemical Formula 1, R ₁ is hydrogen or a methyl group, R ₂ is hydrogen, a straight or branched chain alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, R ₃ and R ₄ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, a, b, and c are natural numbers of 0 to 1, respectively, where a + b + c = 1, 0.1≤ [(a + c) / (a + b + c)] ≤0.5 or 0.1≤ [c / (a + b + c)] ≤ 0.5. The method of claim 2, wherein a, b, and c have a value of 0.20 ≦ [(a + c) / (a + b + c)] ≦ 0.40 or 0.1 ≦ [c / (a + b + c)] ≦ 0.20 A chemically amplified positive photoresist composition having a. The chemically amplified positive photoresist composition according to claim 1, wherein the component (B) is a compound represented by the following Chemical Formula 2. [Formula 2]

In Formula 2, R ₅ and R ₆ are each independently a hydroxy group, an amino group or a C 1-10 straight or branched chain alkyl group unsubstituted or substituted with an alkoxy group having 1 to 6 carbon atoms; A C3-C10 cycloalkyl group unsubstituted or substituted with a hydroxy group, an amino group or a C1-C6 alkoxy group; Or an alkyl group having 1 to 20 carbon atoms, alkoxy having 1 to 6 carbon atoms or an aryl group having 6 to 11 carbon atoms substituted or unsubstituted. The method according to claim 4, in the formula 2, R ₅ and R ₆ are each independently n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4, And a 6-triisopropylphenyl group, a 4-dodecylphenyl group, a 4-methoxyphenyl group, a 2-naphthyl group, or a benzyl group. The chemically amplified positive photoresist composition according to claim 1, wherein the content of the component (B) is 0.1 to 20 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. . The chemically amplified positive photoresist composition according to claim 1, wherein the content of the component (C) comprises 0.1 to 30 parts by weight based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. . The chemically amplified positive photoresist composition of claim 1, wherein R ₇ and R ₈ are each a bond or di (trifluoromethyl) methylene. The chemical amplification according to claim 1, wherein the composition further comprises 0.001 to 10 parts by weight of the nitrogen-containing basic organic compound as a quencher, based on 100 parts by weight of the resin which is soluble in the aqueous alkali solution by the action of an acid. Positive photoresist composition. 10. A resist pattern comprising applying the chemically amplified positive photoresist composition of any one of claims 1 to 9 onto a substrate, prebaking and selectively exposing, followed by heat treatment, and developing with an alkaline developer to form a resist pattern. Formation method.