KR101517763B1 - Dissolution inhibitor and chemically amplified photoresist composition including the same - Google Patents

Abstract

Disclosed is a dissolution inhibitor capable of improving the line edge roughness by increasing the solubility difference between an exposed portion and a non-exposed portion in a photolithography process, and a chemically amplified resist composition comprising the dissolution inhibitor. The dissolution inhibitors include the following formulas (wherein, R ₁ is a linear, branched, single ring, or the alkyl group of the ring-shaped of C1 ~ C30, R ₂ is a linear C1 ~ C20 linear, branched, single ring, or the annular Alkyl group).

The photoresist composition may further comprise 3 to 30% by weight of a photosensitive polymer; A dissolution inhibitor represented by the above formula in an amount of 1 to 30 parts by weight based on 100 parts by weight of the photosensitive polymer; 0.05 to 10 parts by weight of a photoacid generator based on 100 parts by weight of the photosensitive polymer; And the remaining organic solvent.

A dissolution inhibitor, a chemically amplified photoresist composition, a line edge roughness

Description

Dissolution inhibitor and chemically amplified photoresist composition including the same [0002]

The present invention relates to a dissolution inhibitor, and more particularly, to a dissolution inhibitor which can improve the line edge roughness by increasing the difference in solubility between the exposed portion and the non-exposed portion in the formation of a fine pattern using a photolithography process Dissolution inhibitor and a chemically amplified resist composition containing the same.

Generally, a chemically amplified photoresist composition used in a photolithography process includes a photosensitive polymer that reacts with an acid to change its solubility to a developer, a photoacid generator that generates an acid upon irradiation of light (photo-acid generator) and an organic solvent. The acid generated in the exposure part induces the deprotection reaction of the photosensitive polymer, thereby increasing the solubility difference between the exposed part and the non-exposed part. The photoresist composition may further include a dissolution inhibitor which is insoluble in water or a developer so as to make the unexposed portion harder and to form a firm and slope-less photoresist pattern.

Accordingly, an object of the present invention is to provide a dissolution inhibitor which can improve the line edge roughness by increasing the difference in solubility between the exposed portion and the non-exposed portion in a photolithography process using various radiation such as ArF as an exposure source and the like To provide a chemically amplified resist composition.

It is another object of the present invention to provide a method for preparing a resist composition which can control the degree of diffusion of an acid generated by exposure by controlling the amount of a dissolution inhibitor and can improve the affinity with a developer and can improve the line edge roughness And a chemically amplified resist composition containing the same.

In order to achieve the above object, the present invention provides a dissolution inhibitor represented by the following formula:

[Chemical Formula 1]

R ₁ is a linear, branched, monocyclic or polycyclic alkyl group having ₁ to 30 carbon atoms and R ₂ is a linear, branched, monocyclic or polycyclic alkyl group having ₁ to 20 carbon atoms.

Also, the present invention provides a photosensitive composition comprising 3 to 30% by weight of a photosensitive polymer; 1 to 30 parts by weight of a dissolution inhibitor represented by the above formula (1) based on 100 parts by weight of the photosensitive polymer; 0.05 to 10 parts by weight of a photoacid generator based on 100 parts by weight of the photosensitive polymer; And a remaining organic solvent. (A) applying the photoresist composition on a substrate to form a photoresist film; (b) exposing the photoresist film to a predetermined pattern; (c) heating the exposed photoresist film; And (d) developing the heated photoresist film to obtain a desired pattern.

The dissolution inhibitor and the chemically amplified photoresist composition containing the same according to the present invention contain nitrogen atoms in the dissolution inhibitor structure which can increase the difference in solubility between the exposed and unexposed portions in the photolithography process, By controlling the amount of the inhibitor, it is possible to control the degree of diffusion of the acid by exposure. Further, since the hydroxyl group is contained in the structure of the dissolution inhibitor, the affinity with the developer can be increased, and the line edge roughness roughness.

Hereinafter, the present invention will be described in detail.

The dissolution inhibitor according to the present invention has a structure represented by the following formula (1).

In the above formula (1), R ₁ is a linear, branched, monocyclic or polycyclic alkyl group having from 1 to 30 carbon atoms (that is, having from 1 to 30 carbon atoms), wherein R ₁ is a hydroxyl group, a halogen group, R ₂ is a linear, branched, monocyclic or polycyclic alkyl group having from 1 to 20 carbon atoms (that is, having from 1 to 20 carbon atoms), and may optionally be substituted with a halogen group, a hydroxy group, etc. An ether group, an ester group, and the like, and may be, for example, a C5-C10 alkyl group or a cyclic alkyl group containing an ether group or an ester group. Preferably, R ₂ is a branched, monocyclic, or polycyclic, bulky alkyl group.

,

,

,

,

,

등을 예시할 수 있고, 상기 R₂의 구체적인 예로는,

,

,

,

,

,

등을 예시할 수 있다. (여기서,

은 연결부(connecting bond)를 나타낸다)Specific examples of R < ₁ >

,

,

,

,

,

And specific examples of R < ₂ > include, for example,

,

,

,

,

,

And the like. (here,

Represents a connecting bond)

(화학식 1a),

(화학식 1b),

(화학식 1c),

(화학식 1d),

(화학식 1e),

(화학식 1f) 등을 예시할 수 있다.As specific examples of the dissolution inhibitor represented by the formula (1) according to the present invention,

(Formula 1a),

(1b),

(Formula 1c),

(1d),

(1e),

(Formula (1f)), and the like.

The dissolution inhibitor represented by the above-described formula (1) has the same concept as a general dissolution inhibitor because it accelerates dissolution in the exposed part but on the contrary, acts to inhibit dissolution in the unexposed part. Characteristically, the dissolution inhibitor represented by the above-mentioned formula (1) contains nitrogen atoms in the structure, and the degree of dissolution of the acid by exposure can be controlled by controlling the amount of the dissolution inhibitor so that the deprotection reaction of the non- The protective groups of the non-visible portion act as dissolution inhibiting agents. In addition, since it contains a hydroxyl group in the structure, affinity with a developer can be increased, and it is effective in improving line edge roughness.

The dissolution inhibitor represented by Formula 1 according to the present invention can be synthesized as follows. For example, as shown in Reaction Scheme 1 below, a compound having a diisocyanate group and a compound having a hydroxyl group are reacted under a nitrogen condition to produce an intermediate, and the resulting intermediate is reacted with starch to obtain a dissolution inhibitor of the present invention Can be manufactured.

In the above Reaction Scheme 1, R ₁ and R ₂ are as defined in Formula 1 above.

(화학식 2a),

(화학식 2b),

(화학식 2c),

(화학식 2d),

(화학식 2e),

(화학식 2f) 등을 예시할 수 있다.As specific examples of the compound having a diisocyanate group,

(Formula 2a),

(Formula 2b),

(Formula 2c),

(Formula 2d),

(Formula 2e),

(Formula 2f), and the like.

The reaction is carried out by dissolving the reaction product in n-methylpyrrolidine (NMP), adding n-butylamine to the reaction, and after completion of the reaction, the product is washed with methanol The mixture was extracted with methylenechloride, separated, and then filtered through anhydrous magnesium sulfate. The filtrate was placed in a vacuum distillation apparatus, the methylene chloride was evaporated, and the product was purified by column chromatography using silica gel .

The photoresist composition according to the present invention comprises the dissolution inhibitor represented by the above-mentioned formula (1), the photosensitive polymer, the photoacid generator and the organic solvent, and further includes a basic compound, a surfactant and the like as a reaction inhibitor can do.

In the photoresist composition of the present invention, the content of the photosensitive polymer is 3 to 30% by weight, preferably 3 to 15% by weight. The content of the dissolution inhibitor represented by Formula 1 is 1 to 30 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the photosensitive polymer, and the content of the photoacid generator is 100 parts by weight And the remaining component of the photoresist composition is an organic solvent. When a basic compound is used as a reaction inhibitor, the amount of the basic compound used is 0.01 to 10% by weight, preferably 0.01 to 2% by weight based on the total photoresist composition.

If the content of the dissolution inhibitor is too small, it is difficult to sufficiently attain the object of the present invention because the difference in solubility between the exposed portion and the unexposed portion can not be effectively increased. If the content of the dissolution inhibitor is too large, The physical properties of the mixtures may be changed so that the acid generated upon exposure may interfere with the deprotection reaction of the polymer, which ultimately undermines the resolving power of the resist. Furthermore, because of the increased low molecular weight content, the solubility of the polymer mixture also increases, which may lead to dissolution of the unexposed area in the development process after exposure. If the content of the photosensitive polymer is too small, it is difficult to form a resist film having a desired thickness. If the content of the photosensitive polymer is too large, the thickness distribution of the pattern formed on the wafer may become uneven. If the amount of the photoacid generator used is too small, the sensitivity of the photoresist to light is deteriorated. If the amount is too large, the photoacid generator may absorb much of the ultraviolet light and generate an excessive amount of acid, have. If the amount of the basic compound used is too small, the diffusion of the generated acid during the exposure can not be easily controlled and the cross-sectional shape of the pattern may be uneven. If too large, the diffusion of the generated acid may be excessively suppressed, It is not easy.

As the photosensitive polymer, a conventional photosensitive polymer for a photoresist which reacts with an acid to change its solubility in a developing solution can be used without limitation, and it is preferable to use a photosensitive polymer which can be desorbed by an acid, Polymers can be used. The photosensitive polymer may be a block copolymer or a random copolymer, and preferably has a weight average molecular weight (Mw) of 3,000 to 20,000.

As the photoacid generator, a compound capable of generating an acid upon irradiation with light can be used without limitation, and an onium salt commonly used as a photoacid generator of a photoresist composition, such as a sulfonium salt or An iodonium salt-based compound can be used. In particular, it is possible to use phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone and naphthylimido trifluoromethane sulfonate as starting materials. And it is also possible to use those selected from the group consisting of diphenyl iodide salt triflate, diphenyl iodide salt nonaplate, diphenyl iodide salt hexafluorophosphate, diphenyl iodide salt hexafluoroarsenate, diphenyl iodide salt hexafluoroantimo Tetraphenylsulfonium triflate, diphenyl para-methoxyphenylsulfonium triflate, diphenyl para-toluenesulfonium triflate, diphenyl para-tertiary butylphenylsulfonium triflate, diphenyl paraisobutylphenyl sulfonium triflate, triphenylsulfonium triflate, Triflate, triflate, tetrabutylphenylsulfonium triflate, di Diphenyl para-toluenesulfonium nonaplate, diphenyl para-tert-butylphenylsulfonium nonaplate, diphenyl paraisobutylphenylsulfonium nonaplate, triphenylsulfonium nonaplate, A photoacid generator selected from the group consisting of triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, triarylsulfuric anhydride, Can be used.

As the organic solvent, an organic solvent usually used as a solvent for a photoresist composition may be used without limitation. Examples of the organic solvent include ethylene glycol monomethyl ethyl, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoacetate , Diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol, propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamyl ketone, cyclohexanone, di N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-methylpyrrolidone, Methyl 2-pyrrolidone, 3-ethoxyethyl propionate, 2-heptanone, gamma-butyrolactone, 2-hydroxypropionyl ethyl, 2- Ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxy-2-methylpropionate, ethyl 3-ethoxypropionate, 3-methoxy 2 Ethyl ethyl ketone, ethyl acetate, ethyl acetate, butyl acetate, and mixtures thereof.

Examples of the basic compound used as the quencher include triethylamine, triisobutylamine, trioctylamine, triisooctylamine, diethanolamine, triethanolamine, mixtures thereof, and the like . In addition to the above-mentioned photoacid generators (PAG), solvent, and base, it is obvious that a general photoacid generator, a solvent, and a base can be used. The surfactant contained in the photoresist composition according to the present invention, if necessary, is added to improve the homogeneous mixing property of the photoresist composition component, the coating property of the photoresist composition, and the post-exposure developability of the photoresist composition. As such a surfactant, a conventional surfactant used in a photoresist composition may be used without limitation. For example, a fluorine-based surfactant, a fluorine-silicon-based surfactant, and the like may be used. The amount of the surfactant to be used is 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the solid content of the photoresist composition. When the amount of the surfactant is too small, , And if it is too large, the resist properties other than the coating properties such as shape stability and storage stability of the composition may be adversely affected.

In order to form a photoresist pattern using the photoresist composition of the present invention, (i) first, the photoresist composition is applied onto a substrate such as a silicon wafer or an aluminum substrate using a spin coater or the like, Forming a resist film, (ii) exposing the photoresist film to a predetermined pattern, and (iii) baking and developing the exposed photoresist film. The developing solution used in the developing step may be an aqueous alkaline solution obtained by dissolving an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide (TMAH) in a concentration of 0.1 to 10 wt% An appropriate amount of a water-soluble organic solvent such as methanol, ethanol and the like and a surfactant may be added.

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 1-1] Preparation of the compound represented by the formula (3a)

As shown in the following Reaction Scheme 2, 50 g (295.7 mmol) of 1,6-hexamethylene diisocyanate and 2-methyl-2- adamantanol) was dissolved in N-methylpyrrolidine (NMP), n-butylamine was added at 115 ° C, and the reaction was carried out for 6 hours. After completion of the reaction, the reaction mixture was washed with methanol, extracted with methylenechloride, separated, and then filtered through anhydrous magnesium sulfate. The filtrate was put in a vacuum distillation apparatus and the methylene chloride was evaporated. The product was isolated by column chromatography using silica gel (developing solvent, hexane: ethyl acetate (EA) = 1: 1) to obtain a compound represented by ^{{yield: 72.5%, 1 H-NMR} (CDCl 3, internal standard): δ (ppm) 8.00 ( NH, 1H), 3.31 (CH 2, 2H), 2.96 (CH 2, 2H ), 2.29 (H, 2H) , 1.77 (H, 2H), 1.56 (H, 1H), 1.55 (CH 2, 2H), 1.52 (H, 1H), 1.50 (CH 3, 3H), 1.40 (H, _{1H), 1.36 (CH 2,} 2H), 1.31 (H, 1H), 1.30 (CH 2, 2H), 1.29 (CH 2, 4H), 1.18 (H, 1H), 1.14 (H, 1H), 0.65 ( H, 2H).

[Chemical Formula 3]

[Preparation Example 1-2] Preparation of the compound represented by the formula (3b)

The compound represented by Formula 3b was obtained in the same manner as in Preparation Example 1-1 except that 50 g (300.9 mmol) of the compound represented by Formula 2b was used instead of 50 g of the compound represented by Formula 2 ({Yield: 81.7% _{^{, 1 H-NMR (CDCl 3}} , internal standard): δ (ppm) 8.00 ( NH, 1H), 3.54 (CH, 1H), 3.22 (CH, 1H), 2.29 (H, 2H), 1.77 (H, _{2H), 1.66 (CH 2,} 4H), 1.50 (CH 3, 3H), 1.40 (CH 2, 4H), 1.36 (CH 2, 2H), 1.56 (H, 1H), 1.52 (H, 1H), 1.40 (H, IH), 1.31 (H, IH), 1.18 (H, IH), 1.14

(3b)

[Preparation Example 1-3] Preparation of the compound represented by the formula (3c)

The compound represented by Formula 3c was obtained in the same manner as in Preparation Example 1-1 except that 50 g (190.6 mmol) of the compound represented by Formula 2c was used instead of 50 g of the compound represented by Formula 2a (yield: 78.3% _{^{, 1 H-NMR (CDCl 3}} , internal standard): δ (ppm) 8.00 ( NH, 1H), 3.54 (CH, 1H), 3.22 (CH, 1H), 1.66 (CH 2, 4H), 1.50 (CH _{3, 3H), 1.43 (CH} , 2H), 1.40 (CH 2, 12H), 1.36 (CH 2, 2H), 2.29 (H, 2H), 1.77 (H, 2H), 1.40 (CH 2, 4H), _{1.36 (CH 2, 2H),} 1.56 (H, 1H), 1.52 (H, 1H), 1.40 (H, 1H), 1.31 (H, 1H), 1.18 (H, 1H), 1.14 (H, 1H), 0.65 (H, 2H).

[Chemical Formula 3c]

[Preparation Example 1-4] Preparation of the compound represented by the general formula (3d)

The compound represented by Formula (3d) was obtained in the same manner as in Preparation Example 1-1, except that 50 g (225.1 mmol) of the compound represented by Formula (2d) was used instead of 50 g of the compound represented by Formula (2a) {Yield: 76.3% _{^{, 1 H-NMR (CDCl 3}} , internal standard): δ (ppm) 8.00 ( NH, 1H), 3.22 (CH, 1H), 2.88 (CH 2, 2H), 2.29 (H, 2H), 1.50 (CH _{3, 3H), 1.40 (CH} 2, 4H), 1.36 (CH 2, 2H), 1.28 (CH 2, 2H), 1.16 (CH 3, 3H), 1.11 (CH 3, 6H), 1.77 (H, 2H ), 1.56 (H, IH), 1.52 (H, IH), 1.40 (H, IH), 1.31 (H, }.

(3d)

[Preparation Example 1-5] Preparation of a compound represented by the formula (3e)

Compound (3e) was obtained in the same manner as in Preparation Example 1-1 except that 50g (105.8mmol) of the compound represented by Formula (2e) was used instead of 50g of the compound represented by Formula (2a) {Yield: 71.3% _{^{, 1 H-NMR (CDCl 3}} , internal standard): δ (ppm) 8.00 ( NH, 1H), 7.05 (H, 1H), 5.25 (CH 2, 4H), 4.98 (H, 1H), 3.31 (CH _{2, 2H), 2.29 (H} , 2H), 1.77 (H, 2H), 1.52 (CH, 2H), 1.56 (H, 1H), 1.52 (H, 1H), 1.50 (CH 3, 3H), 1.40 ( H, 1H), 1.36 (CH 2, 2H), 1.33 (CH 2, 4H), 1.31 (H, 1H), 1.30 (CH 2, 2H), 1.29 (CH 2, 20H), 1.25 (CH 2, 6H _{), 0.96 (CH 3, 6H} ), 1.18 (H, 1H), 1.14 (H, 1H), 0.65 (H, 2H)}.

[Formula 3e]

[Preparation Example 1-6] Preparation of the compound represented by the formula (3f)

Compound (3f) was obtained in the same manner as in Preparation Example 1-1 except that 50g (160.2mmol) of the compound represented by Formula (2f) was used instead of 50g of the compound represented by Formula (2a) {Yield: 82.6% _{^{, 1 H-NMR (CDCl 3}} , internal standard): δ (ppm) 8.00 ( NH, 1H), 3.63 (H, 2H), 3.28 (H, 2H), 2.29 (H, 2H), 1.77 (H, 2H) 1.56 (H, 1H) , 1.52 (H, 1H), 1.50 (CH 3, 3H), 1.40 (H, 1H), 1.36 (CH 2, 2H), 1.31 (H, 1H), 1.18 (H, 1H), 1.14 (H, 1 H), 0.65 (H, 2H)}.

(3f)

[Example 1-1] Preparation of dissolution inhibitor represented by formula (Ia)

As shown in Scheme 3, 50 g (149.5 mmol) of the compound represented by the general formula (3a) and 50 g (260.1 mmol) of starch were dissolved in n-methylpyrrolidone, and then n-butylamine And reacted for 4 hours. After completion of the reaction, the reaction solution was washed with methanol, extracted with methylene chloride, separated, and then filtered through anhydrous magnesium sulfate. The filtrate was put in a vacuum distillation apparatus and the methylene chloride was evaporated. The product was isolated by column chromatography using silica gel (developing solvent, hexane: ethyl acetate (EA) = 1: 1) to obtain a white solid dissolution inhibitor to give the compound (formula 1a) ^{{yield: 53.7%, 1 H-NMR} (CDCl 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 4.51 (CH, 1H), 4.21 (CH 2, 2H) , 3.85 (CH, 1H), 3.73 (CH, 1H), 3.40 (CH, 1H), 3.24 (CH 3, 3H), 3.02 (CH, 2H), 2.96 (CH 2, 4H), 2.00 (OH, 2H _{), 1.55 (CH 2, 4H} ), 1.50 (CH 3, 3H), 1.36 (CH 2, 2H), 1.29 (CH 2, 4H), 1.21 (CH 3, 3H), 2.29 (H, 2H), 1.77 (H, 2H), 1.56 ( H, 1H), 1.55 (CH 2, 2H), 1.52 (H, 1H), 1.40 (H, 1H), 1.36 (CH 2, 2H), 1.31 (H, 1H), _{1.30 (CH 2, 2H),} 1.29 (CH 2, 4H), 1.18 (H, 1H), 1.14 (H, 1H), 0.65 (H, 2H)}.

[Formula 1a]

[Example 1-2] Preparation of dissolution inhibitor represented by formula (1b)

The dissolution inhibitor represented by the general formula (1b) was obtained in the same manner as in Example 1-1 except that 50 g (150.9 mmol) of the compound represented by the general formula (3b) was used instead of the compound represented by the general formula (3a) ^{%, 1 H-NMR (CDCl} 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 4.51 (CH, 1H), 4.21 (CH 2, 2H), 3.85 (CH, 1H), 3.73 ( CH, 1H), 3.54 (CH , 2H), 3.40 (CH, 1H), 3.24 (CH 3, 3H), 3.02 (CH, 2H), 2.00 (OH, 2H), 1.50 (CH 3, 3H), 1.36 _{(CH 2, 2H), 1.21} (CH 3, 3H), 2.29 (H, 2H), 1.77 (H, 2H), 1.56 (H, 1H), 1.52 (H, 1H), 1.40 (H, 1H), 1.31 (H, 1 H), 1.18 (H, 1 H), 1.14 (H, 1 H), 0.65 (H, 2H)}.

[Chemical Formula 1b]

[Example 1-3] Preparation of dissolution inhibitor represented by formula (1c)

A dissolution inhibitor represented by the formula (1c) was obtained in the same manner as in Preparation Example 1-1, except that 50 g (166.9 mmol) of the compound represented by the formula (3c) was used instead of 50 g of the compound represented by the above formula (3a) {Yield: 62.1 ^{%, 1 H-NMR (CDCl} 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 4.51 (CH, 1H), 4.21 (CH 2, 2H), 3.85 (CH, 1H), 3.73 ( 2H), 1.66 (CH ₂ , 8H), 1.50 (CH ₃ , 3H), 3.04 _{(CH 3, 3H), 1.43} (CH, 1H), 1.40 (CH 2, 8H), 1.36 (CH 2, 2H), 1.21 (CH 3, 3H), 1.21 (CH, 2H), 1.16 (CH 3, _{3H), 1.11 (CH 3,} 6H), 2.29 (H, 2H), 1.77 (H, 2H), 1.56 (H, 1H), 1.52 (H, 1H), 1.40 (H, 1H), 1.31 (H, 1H), 1.18 (H, 1 H), 1.14 (H, 1 H), 0.65 (H, 2H)}.

[Chemical Formula 1c]

[Example 1-4] Preparation of dissolution inhibitor represented by formula (1d)

A dissolution inhibitor represented by the formula (1d) was obtained in the same manner as in Preparation Example 1-1 except that 50 g (129.1 mmol) of the compound represented by the formula (3) was used in place of the compound (3) represented by the formula (3a) {Yield: 56.1 ^{%, 1 H-NMR (CDCl} 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 4.51 (CH, 1H), 4.21 (CH 2, 2H), 3.85 (CH, 1H), 3.73 ( CH, 1H), 3.54 (CH , 2H), 3.40 (CH, 1H), 3.24 (CH 3, 3H), 3.02 (CH, 1H), 3.02 (CH, 2H), 2.00 (OH, 2H), 1.58 ( _{CH 2, 4H), 1.50 (} CH 3, 3H), 1.36 (CH 2, 2H), 1.28 (CH 2, 2H), 1.21 (CH 3, 3H), 1.16 (CH 3, 3H), 1.11 (CH 3 1H, 1H), 1.18 (2H, m), 2.32 (2H, 1H), 1.14 (H, 1 H), 0.65 (H, 2H)}.

≪ RTI ID = 0.0 &

[Example 1-5] Preparation of dissolution inhibitor represented by the formula (1e)

A dissolution inhibitor represented by the formula (1e) was obtained in the same manner as in Preparation Example 1-1 except that 50 g (78.4 mmol) of the compound represented by the formula (3e) was used instead of the compound represented by the formula (3a) ^{%, 1 H-NMR (CDCl} 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 5.25 (CH 2, 2H), 4.98 (H, 1H), 4.51 (CH, 1H), 4.21 ( _{CH 2, 2H), 3.85 (} CH, 1H), 3.73 (CH, 1H), 3.40 (CH, 1H), 3.24 (CH 3, 3H), 3.02 (CH, 2H), 2.96 (CH 2, 2H), 2.00 (OH, 2H), 1.55 (CH 2, 4H), 1.52 (CH, 2H), 1.50 (CH 3, 3H), 1.47 (CH 2, 4H), 1.36 (CH 2, 2H), 1.33 (CH 2 _{, 4H), 1.29 (CH 2} , 20H), 1.25 (CH 2, 6H), 1.21 (CH 3, 3H), 1.16 (CH 3, 3H), 1.11 (CH 3, 6H), 2.29 (H, 2H) (H, IH), 1.34 (H, IH), 1.77 (H, _{0.96 (CH 3, 6H),} 0.65 (H, 2H)}.

[Formula 1e]

[Example 1-6] Preparation of the dissolution inhibitor represented by the formula (1f)

The dissolution inhibitor represented by the formula (1f) was obtained in the same manner as in Preparation Example 1-1 except that 50g (78.4mmol) of the compound represented by the formula (3f) was used instead of 50g of the compound represented by the above formula (3a) {Yield: 49.6 ^{%, 1 H-NMR (CDCl} 3, internal standard): δ (ppm) 8.00 ( NH, 2H), 4.51 (CH, 1H), 4.21 (CH 2, 2H), 3.85 (CH, 1H), 3.73 ( CH, 1H), 3.40 (CH , 1H), 3.28 (H, 4H), 3.24 (CH 3, 3H), 3.02 (CH, 1H), 2.00 (OH, 2H), 1.50 (CH 3, 3H), 1.36 _{(CH 2, 2H), 1.21} (CH 3, 3H), 2.29 (H, 2H), 1.77 (H, 2H), 1.56 (H, 1H), 1.52 (H, 1H), 1.40 (H, 1H), 1.31 (H, 1 H), 1.18 (H, 1 H), 1.14 (H, 1 H), 0.65 (H, 2H)}.

(1f)

[Examples 2-1 to 2-6] Photoresist composition and exposure pattern formation

, 0.2 g of the dissolution inhibitor synthesized in Examples 1-1 to 1-6, 2.0 g of photosensitive polymer (MAdMA: GBLMA: HMA = 40: 30: 30, Mw = 8,000, PD = 1.92) 0.08 g of triphenylsulfonium triplate, 0.02 g of triethanolamine (TEA) as a reaction inhibitor and 20 g of propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent were mixed and filtered with a filter To prepare respective photoresist compositions. The prepared photoresist composition was spin-coated on top of the etching layer of a silicon wafer to form a photoresist thin film and then prebaked at 130 캜 for 90 seconds to obtain ArF ASML 1250 having a numerical aperture of 0.85 (PEB, Post exposure bake) at 125 캜 for 90 seconds. The thus-baked wafer was developed with an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide (TMAH) for 30 seconds to form a 1: 1 line and a space (L / S: line / space) pattern of 65 nm. The performance of the thus formed photoresist pattern was evaluated and shown in Table 1 below. In Table 1, the focus depth (focus margin, μm) is defined as the process margin, the depth of the exposure amount irradiated to the resist film, the EOP is the optimal exposure amount (mJ / cm ² ) It is the amount of exposure that can obtain the pattern size.

Example Minimum resolution [nm] Depth of focus [um] EOP [mJ / cm ² ] Line edge
Roughness [nm] Example 2-1 60.5 0.61 26 3.01 Example 2-2 61.8 0.64 27 3.21 Example 2-3 60.3 0.55 23 3.07 Examples 2-4 63.7 0.60 29 2.98 Example 2-5 62.9 0.62 30 2.87 Examples 2-6 65.4 0.65 32 2.97

It can be seen from Table 1 that a resolution of 66 nm or less can be obtained when patterning is performed using the resist composition according to the present invention and a mask having a resolution of 65 nm (Examples 2-1 to 2-6) When the composition is used, the line edge roughness shows a value of 5 to 6 nm. However, when the composition according to the present invention is used, the line edge roughness shows a value of 2.87 to 3.21 nm, . As a result of exposing the mask to a wafer using an extreme ultraviolet (EUV) exposure equipment, the same line and space pattern of 30 nm could be successfully formed using the photoresist composition of the present invention.

Claims (8)

1. A dissolution inhibitor represented by the following formula (1). [Chemical Formula 1]

Herein, R ₁ is a linear, branched or cyclic alkyl group having ₁ to 30 carbon atoms, and R ₂ is a C1 to C20 branched, monocyclic or polycyclic alkyl group. delete 2. The compound of claim ₁ wherein R < ₁ >

,

,

,

,

, And

And R < ₂ > is selected from the group consisting of hydrogen,

,

,

,

,

, And

≪ / RTI > (here,

Represents a connecting bond) The dissolution inhibitor according to claim 1, wherein the dissolution inhibitor is selected from the group consisting of the following formulas (1a) to (1f). [Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

3 to 30% by weight of a photosensitive polymer; 1 to 30 parts by weight of a dissolution inhibitor represented by the following general formula (1) based on 100 parts by weight of the photosensitive polymer, [Chemical Formula 1]

Wherein R ₁ is a linear, branched or cyclic alkyl group having ₁ to 30 carbon atoms and R ₂ is a branched or cyclic alkyl group having ₁ to 20 carbon atoms; 0.05 to 10 parts by weight of a photoacid generator based on 100 parts by weight of the photosensitive polymer; 0.01 to 10% by weight, relative to the total photoresist composition, of a basic compound; And And the remaining organic solvent. The photoresist composition according to claim 5, wherein the photosensitive polymer has an acid-sensitive protecting group which is cleaved by an acid. 3 to 30% by weight of a photosensitive polymer; 1 to 30 parts by weight of a dissolution inhibitor represented by the following general formula (1) based on 100 parts by weight of the photosensitive polymer, [Chemical Formula 1]

Wherein R ₁ is a linear, branched or cyclic alkyl group having ₁ to 30 carbon atoms and R ₂ is a branched or cyclic alkyl group having ₁ to 20 carbon atoms; 0.05 to 10 parts by weight of a photoacid generator based on 100 parts by weight of the photosensitive polymer; 0.01 to 10% by weight, relative to the total photoresist composition, of a basic compound; 0.001 to 2 parts by weight of a surfactant based on 100 parts by weight of the solid content of the photoresist composition; And And the remaining organic solvent. (a) 3 to 30% by weight of a photosensitive polymer; Wherein R ₁ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, R ₂ is a C1 to C20 branched, monocyclic, or cyclic alkyl group having 1 to 30 carbon atoms, Or a polycyclic alkyl group); [Chemical Formula 1]

0.05 to 10 parts by weight of a photoacid generator based on 100 parts by weight of the photosensitive polymer; 0.01 to 10% by weight, relative to the total photoresist composition, of a basic compound; And a remaining organic solvent on the substrate to form a photoresist film; (b) exposing the photoresist film to a predetermined pattern; (c) heating the exposed photoresist film; And (d) developing the heated photoresist film to obtain a desired pattern.