KR100787854B1 - Acrylate monomer for photoresist, polymer thereof and photoresist composition including the same - Google Patents

Abstract

A sulfonyl group-containing acrylic photoresist monomer is provided to ensure improved resolution and process margin of a photoresist pattern, to improve the focus depth margin and line edge roughness of a photoresist film, and to obtain a fine photoresist pattern by virtue of high dry etching resistance and PEB stability. A sulfonyl group-containing acrylic photoresist monomer is represented by the following formula 1. In formula 1, each of R* and R' independently represents H or methyl; each of R, R1, R2, R3 and R4 independently represents H, a C1-C20 alkyl, ketone, C4-C20 cycloalkyl or multicycloalkyl; and R5 is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, hexyl, phenyl, benzyl, toluene, xylene, perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl and perfluorooctyl.

Description

Acrylic monomer for photoresist, polymer and photoresist composition comprising the same

1 is a graph showing the depth of focus of the photoresist composition prepared in Examples and Comparative Examples of the present invention.

Figure 2 is a graph showing the photospeed of the photoresist composition prepared in Examples and Comparative Examples of the present invention.

The present invention relates to an acrylic photoresist monomer, a polymer, and a photoresist composition comprising the same, and more particularly, to an acrylic photoresist monomer, a polymer including a sulfonyl group, and a photoresist composition including the same.

In recent years, with the high integration and high precision of semiconductor devices, the formation of ultra-fine photoresist patterns of less than 90 nm in pitch is required in a photo lithography process. As a result, while the wavelength of the mass production exposure source is shortened to less than 193 nm, the development of a technique for further optimizing and refinement of the wafer wafer processing process is in progress. In order to realize such a precise pattern, a photosensitive material having low line edge roughness, low post exposure baking sensitivity, and excellent dry etching resistance is required.

In the process of forming the photoresist pattern, in order to improve the resolution, depth of focus and process margin and to form a more precise pattern, a protecting group which is attached to the side chain of the photoresist polymer and suppresses dissolution in the basic solution It is preferable to lower the activation energy of the reaction to be deprotected or to use a material having a low post-exposure bake temperature sensitivity, that is, a material that is less affected by acid. Therefore, when the polymer which has little influence of an acid and whose main chain is decomposed by the light source to expose can be used, the outstanding pattern can be obtained.

Therefore, an object of the present invention can improve the photospeed, resolution and process margin in the semiconductor process, it is possible to implement a precise pattern because the low baking temperature sensitivity after exposure, and to improve the depth of focus margin and line edge roughness It is to provide a photoresist monomer, a polymer and a photoresist composition comprising the same.

Still another object of the present invention is to provide a method of forming a photoresist pattern using the photoresist composition.

In order to achieve the above object, the present invention provides a (meth) acrylate monomer having a sulfonyl group represented by the following formula (1).

또는

or

In Formula 1, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

In addition, the present invention provides a chemically amplified photosensitive polymer represented by the following formula (4) capable of generating a secondary acid in the post-exposure bake process by the acid generated by the light source.

또는

or

In Formula 4, R ^* and R ^' is Each independently hydrogen or methyl; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; a, b, c and d are mol% of the repeating unit which comprises the said polymer, and are each independently 1-95 mol%.

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

The photoresist monomer containing a sulfonyl group according to the present invention is represented by the following formula (1).

[Formula 1]

또는

or

In Formula 1, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl group or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or multicycloalkyl group having 4 to 20 carbon atoms. Here, two substituents selected from R ₁ , R ₂ , R _3, and R ₄ may be linked to each other to form a ring. For example, R ₃ and R ₄ may be connected to each other to form a cyclopropane, or R ₂ And R ₄ may be linked to each other to form cyclobutane. R ₅ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, n-propyl group, isopropyl group, n Butyl group, t-butyl group, hexyl group, phenyl group, benzyl group, toluene group, xylene group, perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group or perfluorooctyl group to be.

In the photosensitive monomer represented by Chemical Formula 1 according to the present invention, not only the deprotection reaction is carried out by an acid catalyst like a conventional deprotection group, but also an acid (primary acid) generated from a photoacid generator (PAG). To generate a secondary acid in the baking process. That is, by amplifying the primary acid to form a secondary acid, the deprotection reaction can proceed by an effective deprotection action even with the generation of a small amount of acid. Therefore, it is possible to form a fine pattern with a small exposure amount, and to improve not only the depth of focus margin and the resolution but also the process margin.

The photoresist polymer may include a monomer of Formula 1 and three or more conventional monomers, as shown in Formula 4 below, and preferred examples thereof are the same as in Formulas 4a to 4h.

[Formula 4]

또는

or

In Formula 4, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; a, b, c and d are mole% of the repeating units constituting the polymer, each independently 1 to 95 mole%, preferably a: b: c: d is 1 to 30 mole%: 30 to 50 Mol%: 20-40 mol%: 25-40 mol%.

In Formulas 4a to 4h, R ^* , a, b, c, and d are as defined in Formula 4. In addition, the photosensitive polymer may further include other monomers, crosslinkable monomers, and the like, which are commonly used in the preparation of the photosensitive polymer, in addition to the above-mentioned monomers, and the content of these auxiliary monomers is usually 0 to about all the repeating units. 5 mol%. The photosensitive polymer according to the present invention may be a block copolymer or a random copolymer, and the weight average molecular weight (Mw) is preferably 3,000 to 100,000, more preferably 3,000 to 15,000. It is preferable that it is 1.0-5.0, and, as for Polydispersity, it is more preferable that it is 1.0-2.2. When the weight average molecular weight and the dispersion degree are outside the above ranges, the physical properties of the photoresist film may be lowered, or the formation of the photoresist film may be difficult, and the contrast of the pattern may be lowered.

Production of the (meth) acrylate photosensitive monomer having a sulfonyl group in the molecule of the present invention includes, for example, a) quantitative measurement of a compound having a vinyl group and an m-chloroperoxybenzoic acid (hereinafter referred to as 'mCPBA'). Epoxidation of the vinyl group by reaction (see Scheme 1 below), b) synthesis of an acrylate compound through reaction with (meth) acrylic acid (see Scheme 2 below), and c) again triethylamine, pyridine Under a base such as the above, it can be made by reacting with a sulfonyl compound in a conventional organic solvent such as THF at room temperature and atmospheric pressure (see Scheme 3 below).

Referring to the method of manufacturing the photosensitive monomer according to the present invention exemplified above in more detail as follows.

First, as shown in following Reaction Formula 1, a vinyl compound is put into a reactor, and reaction temperature is made 0 degreeC. To this, mCPBA is slowly added dropwise, the temperature of the reactor is raised to room temperature, and then reacted in a conventional organic solvent such as methylene chloride, methanol, ethanol, THF and the like for 12 hours at normal pressure.

Scheme 1

Then, as shown in Scheme 2 below, (meth) acrylic acid was added to the compound synthesized in Scheme 1 at a temperature of 0 ° C. and atmospheric pressure, and then the temperature of the reactor was raised to room temperature, followed by acetone, THF for 12 hours. The reaction is carried out in a conventional organic solvent such as.

Scheme 2

Finally, as shown in Scheme 3 below, after triethylamine was added to the compound synthesized in Scheme 2, a sulfonyl chloride compound was added at a temperature of 0 ° C. and atmospheric pressure, and then the temperature of the reactor was raised to room temperature. The reaction is carried out in a conventional organic solvent such as pyridine and THF for 12 hours.

Scheme 3

The polymer represented by Chemical Formula 4 according to the present invention may be prepared by a conventional polymerization reaction using the monomer represented by Chemical Formula 1 and other monomers, and as the initiator, a wide range of polymerization initiators commonly known in the art may be used. Azobis (isobutylonitrile) (AIBN) etc. can be illustrated without limitation.

The photoresist composition of the present invention includes a photosensitive polymer comprising a monomer represented by the formula (1), a photoacid generator for generating an acid and an organic solvent, and can be prepared by mixing various additives as necessary. It is preferable to make solid content concentration of the manufactured photoresist composition into 1 to 30 weight% with respect to the whole photoresist composition, and it is used, filtering by a 0.2 micrometer filter etc.

The photoacid generator may be used as long as it is a compound capable of generating an acid by light, and non-limiting examples may include onium salt, organic sulfonic acid, or a mixture thereof. The content of the photoacid generator is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total photoresist polymer. If the photoacid generator is added in less than 0.1 parts by weight, the sensitivity of the photoresist composition to light is lowered. If the photoresist is used in excess of 20 parts by weight, the photoacid generator absorbs a lot of ultraviolet rays and a large amount of acid is generated. There is a risk of poor quality.

As the organic solvent constituting the photoresist composition according to the present invention can be used a wide variety of organic solvents commonly used in the preparation of the photoresist composition, non-limiting examples include ethylene glycol monomethyl ethyl, ethylene glycol monoethyl ether , Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-hydroxypropionethyl, 2-hydroxy 2-methyl Ethyl propionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy 3-methyl butyrate, methyl 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate , Ethyl acetate, butyl acetate, or a mixture thereof can be exemplified. The content of the organic solvent is preferably 300 to 5000 parts by weight based on 100 parts by weight of the total photoresist polymer.

In addition, the photoresist composition of the present invention may further include an organic base, the content of the organic base is 0.01 to 10% by weight. As the organic base, triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanolamine or mixtures thereof may be used.

In order to form a photoresist pattern using the photoresist composition of the present invention, first, the photoresist composition is coated on a etched layer such as a silicon wafer or an aluminum substrate using a spin coater to form a photoresist film. After exposing the photoresist film in a predetermined pattern, the exposed photoresist film may be heated and developed to obtain an excellent pattern. As a developing solution used in the developing step, an alkaline aqueous solution in which alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate and tetramethylammonium hydroxide (TMAH) are dissolved at a concentration of 0.1 to 10% by weight may be used. A proper amount of water-soluble organic solvent and surfactant, such as methanol and ethanol, can be added to the. In addition, after developing with a developing solution, it is washed with ultrapure water.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited by the following examples.

Example 1-1 Synthesis of Compound Represented by Formula 1a

19.3 g (0.20 mol) of 1-methyl cyclohexene was mixed with 150 g of methylene chloride in a 500 mL flask, and the reaction temperature was 0 ° C. 38.0 g (0.22 mol) of mCPBA was slowly dripped at this solution, and it was made to react for 6 hours. After the reaction was completed, the reaction was filtered under reduced pressure and washed three times with 300 mL of distilled water. The reaction was dried to give 20.6 g of the compound represented by Formula 1a (yield 92%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.90 (CH, 1H), 1.54 (CH ₂ , 2H), 1.50 (CH ₂ , 2H), 1.25 (CH ₃ , 3H), 1.20 ( CH ₂ , 4H)

Example 1-2 Synthesis of Compound Represented by Formula 1b

A compound represented by the following Chemical Formula 1b was prepared in the same manner as in Example 1-1, except that 22.0 g (0.20 mol) of 1,3-dimethyl-cyclohexene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene. 21.4g was obtained (yield 85%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.89 (CH, 1H), 1.91 (CH, 1H), 1.50 (CH ₂ , 2H), 1.24 (CH ₃ , 3H), 1.21 (CH ₂ , 2H), 1.19 (CH ₂ , 2H), 0.96 (CH ₃ , 3H)

Example 1-3 Synthesis of Compound Represented by Formula 1c

In the same manner as in Example 1-1, except that 27.6 g (0.20 mol) of 4-isopropyl-1-methyl-cyclohexene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene, 28.1g of obtained compounds were obtained (yield 91%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.91 (CH, 1H), 1.78 (CH, 1H), 1.55 (CH ₂ , 2H), 1.51 (CH ₂ , 2H), 1.38 (CH , 1H), 1.36 (CH ₂ , 2H), 1.31 (CH ₃ , 3H), 0.88 (CH ₃ , 6H)

Example 1-4 Synthesis of Compound Represented by Chemical Formula 1d

The same method as Example 1-1 except that 27.6 g (0.20 mol) of 1- (4-methyl-cyclohexa-3-enyl) -ethanone was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene. Thus, 28.4 g of a compound represented by the following Chemical Formula 1d was obtained (yield 92%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.90 (CH, 1H), 2.24 (CH ₃ , 3H), 1.94 (CH ₃ , 3H), 1.72 (CH ₂ , 2H), 1.61 ( CH ₂ , 2H), 1.55 (CH ₂ , 2H), 1.28 (CH ₃ , 3H)

Example 1-5 Synthesis of Compound Represented by Chemical Formula 1e

23.5 g of the compound represented by the following Chemical Formula 1e in the same manner as in Example 1-1, except that 22.0 g (0.20 mol) of vinyl methyl-cyclohexene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene. Obtained (yield 93%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.55 (CH, 1H), 2.51 (CH ₂ , 2H), 1.78 (CH, 1H), 1.21 (CH ₂ , 4H), 1.11 (CH ₂ , 4H), 1.08 (CH ₂ , 2H)

Example 1-6 Synthesis of Compound Represented by Chemical Formula 1f

25.5 g of the compound represented by the following formula (1f) in the same manner as in Example 1-1, except that 24.8 g (0.20 mol) of isophenyl methyl-cyclohexene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene Obtained (yield 91%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.48 (CH ₂ , 2H), 1.76 (CH, 1H), 1.35 (CH ₃ , 3H), 1.20 (CH ₂ , 4H), 1.09 ( CH ₂ , 4H), 1.07 (CH ₂ , 2H)

Example 1-7 Synthesis of Compound Represented by Chemical Formula 1g

Example 1- except that 27.2 g (0.20 mol) of 3,7,7-trimethyl-bicyclo [4.1.0] hept-2-ene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene. In the same manner as in 1, 27.4 g of a compound represented by the following formula (1 g) was obtained (yield 90%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 2.92 (CH, 1H), 1.71 (CH, 1H), 1.54 (CH ₂ , 2H), 1.31 (CH, 1H), 1.29 (CH ₃ , 3H), 1.26 (CH ₂ , 2H), 1.02 (CH ₃ , 6H)

Example 1-8 Synthesis of Compound Represented by Chemical Formula 1h

Example 1-1 except that 27.2 g (0.20 mol) of 2,6,6-trimethyl-bicyclo [3.1.1] hept-2-ene was used instead of 19.3 g (0.20 mol) of 1-methyl cyclohexene. 26.8g of the compound represented by the following Chemical Formula 1h was obtained in the same manner as the yield (88%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 3.68 (CH, 1H), 1.88 (CH, 1H), 1.78 (CH, 1H), 1.64 (CH, 1H), 1.60 (CH ₂ , 2H), 1.28 (CH ₃ , 3H), 0.99 (CH ₃ , 6H)

Example 2-1 Synthesis of Compound Represented by Chemical Formula 2a

11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane and 100 g of purified acetone obtained in Example 1-1 were mixed in a 500 mL flask, and the reaction temperature was 0 ° C. 10.3 g (0.12 mol) of (meth) acryloyl acetic acid was slowly added dropwise to this solution, and then the temperature of the reactor was raised to room temperature and reacted for 12 hours. After completion of the reaction, 500 mL of diethyl ether was added to the reaction, and then the unreacted product was removed using a saturated aqueous sodium carbonate solution. After separating the water layer, water was removed using anhydrous magnesium sulfate, and distilled under reduced pressure to obtain 16.0 g of a compound represented by the formula (2a) (yield 81%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.06 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 3.99 (CH, 1H), 2.15 (OH, 1H), 1.86 (CH ₃ , 3H), 1.64 (CH ₂ , 2H), 1.54 (CH ₂ , 2H), 1.26 (CH ₃ , 3H), 1.20 (CH ₂ , 4H)

Example 2-2 Synthesis of Compound Represented by Chemical Formula 2b

1,5-dimethyl-7-oxa-bicyclo [4.1.0] heptane 12.6 obtained in Example 1-2 instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane Except for using g (0.10 mol), in the same manner as in Example 2-1, 17.6 g of a compound represented by the following formula (2b) was obtained (yield 83%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.08 (CH ₂ , 1H), 5.51 (CH ₂ , 1H), 3.94 (CH, 1H), 2.12 (OH, 1H), 1.89 (CH , 1H), 1.48 (CH ₂ , 2H), 1.22 (CH ₃ , 3H), 1.20 (CH ₂ , 2H), 1.18 (CH ₂ , 2H), 0.96 (CH ₃ , 3H)

Example 2-3 Synthesis of Compound Represented by Chemical Formula 2c

4-Isopropyl-1-methyl-7-oxa-bicyclo [4.1.0 obtained in Example 1-3 instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane ] 19.0g of compounds represented by the following Chemical formula 2c was obtained in the same manner as in Example 3-1 except that 15.4 g (0.10 mol) of heptane was used (yield 79%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.02 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 3.92 (CH, 1H), 2.20 (OH, 1H), 1.82 (CH , 1H), 1.52 (CH ₂ , 2H), 1.48 (CH ₂ , 2H), 1.37 (CH, 1H), 1.34 (CH ₂ , 2H), 1.29 (CH ₃ , 3H), 0.89 (CH ₃ , 6H)

Example 2-4 Synthesis of Compound Represented by Chemical Formula 2d

1- (6-methyl-7-oxa-bicyclo [4.1.0] hept obtained in Example 1-4 instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane 17.3 g of a compound represented by the following Chemical Formula 2d was obtained in the same manner as in Example 2-1, except that 15.4 g (0.10 mol) of 3-yl) -ethanone was used (yield 72%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.04 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 3.91 (CH, 1H), 2.21 (CH ₃ , 3H), 2.18 ( OH, 1H), 1.93 (CH ₃ , 3H), 1.71 (CH ₂ , 2H), 1.59 (CH ₂ , 2H), 1.56 (CH ₂ , 2H), 1.27 (CH ₃ , 3H)

Example 2-5 Synthesis of Compound Represented by Chemical Formula 2e

12.6 g (0.10 mol) of 2-cyclohexyl-oxirane obtained in Example 1-5 was used instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane. In the same manner as in Example 2-1, 19.5 g of a compound represented by the following formula (2e) was obtained (yield 92%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.08 (CH ₂ , 1H), 5.51 (CH ₂ , 1H), 3.94 (CH, 1H), 2.58 (CH, 1H), 2.51 (CH , 1H), 2.16 (OH, 1H), 1.77 (CH, 1H), 1.20 (CH ₂ , 4H), 1.09 (CH ₂ , 4H), 1.05 (CH ₂ , 2H)

Example 2-6 Synthesis of Compound Represented by Chemical Formula 2f

14.0 g (0.10 mol) of 2-cyclohexyl-2-methyl-oxirane obtained in Example 1-6 was used instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane. Except that 19.9g of the compound represented by the following formula (2f) was obtained in the same manner as in Example 2-1 (yield 88%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.08 (CH ₂ , 1H), 5.51 (CH ₂ , 1H), 4.24 (CH, 1H), 2.38 (CH, 1H), 2.18 (OH , 1H), 1.76 (CH, 1H), 1.35 (CH ₃ , 3H), 1.20 (CH ₂ , 4H), 1.09 (CH ₂ , 4H), 1.07 (CH ₂ , 2H)

Example 2-7 Synthesis of Compound Represented by Chemical Formula 2g

4,8,8-trimethyl-3-oxa-tricyclo [5.1.1.0 ² obtained in Example 1-7 instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane ^{, 4} ] 17.9 g of a compound represented by the following formula (2g) was obtained in the same manner as in Example 2-1, except that 15.2 g (0.10 mol) of octane was used (yield 75%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.06 (CH 2, 1H), 5.50 (CH ₂ , 1H), 4.10 (CH, 1H), 2.21 (OH, 1H), 1.71 (CH, 1H), 1.54 (CH ₂ , 2H), 1.31 (CH, 1H), 1.29 (CH ₃ , 3H), 1.26 (CH ₂ , 2H), 1.02 (CH ₃ , 6H)

Example 2-8 Synthesis of Compound Represented by Formula 2h

2,7,7-trimethyl-3-oxa-tricyclo [4.1.1.0 ² obtained in Example 1-8 instead of 11.2 g (0.10 mol) of 1-methyl-7-oxa-bicyclo [4.1.0] heptane ^{, 4} ] 17.9 g of a compound represented by the following formula (2h) was obtained in the same manner as in Example 2-1, except that 15.2 g (0.10 mol) of octane was used (yield 75%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 6.10 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 4.25 (CH, 1H), 2.35 (OH, 1H), 1.87 (CH , 1H), 1.77 (CH, 1H), 1.64 (CH, 1H), 1.59 (CH ₂ , 2H), 1.29 (CH ₃ , 3H), 0.98 (CH ₃ , 6H)

Example 3-1 Synthesis of Monomer Represented by Chemical Formula 3a 500 mL of 19.8 g (0.10 mol) and 100 g of acetone in 2-methyl-acrylic acid 2-hydroxy-2methyl-cycloester obtained in Example 2-1 The mixture was mixed in a flask and the reaction temperature was 0 deg. 12.1 g (0.12 mol) of triethylamine was added to the solution, followed by reaction for 1 hour. To this was slowly added dropwise 20.7 g (0.12 mol) of paratoluene sulfonyl chloride using a solid dropping funnel. After raising the temperature of the reactor to room temperature, the reaction was carried out for 12 hours. After the reaction was completed, the reactant was precipitated in excess of deionized water, and dried under reduced pressure to obtain 23.9 g of a monomer represented by the following Chemical Formula 3a (yield 68%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.81 (CH, 2H), 7.32 (CH, 2H), 6.07 (CH ₂ , 1H), 5.48 (CH ₂ , 1H), 4.00 (CH , 1H), 2.32 (CH ₃ , 3H), 1.86 (CH ₃ , 3H), 1.64 (CH ₂ , 2H), 1.54 (CH ₂ , 2H), 1.26 (CH ₃ , 3H), 1.20 (CH ₂ , 4H )

Example 3-2 Synthesis of Monomer Expressed by Chemical Formula 3b

2-methyl-acrylic acid 2-hydroxy-2-methyl-cyclo ester 2-methyl-acrylic acid 2-hydroxy-2,6-dimethyl-cyclo obtained in Example 2-2 instead of 19.8 g (0.10 mol) Except that 21.2 g (0.10 mol) of ester was used, 25.3 g of compounds represented by the following general formula (3b) were obtained in the same manner as in Example 3-1 (yield 69%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.82 (CH, 2H), 7.37 (CH, 2H), 6.04 (CH ₂ , 1H), 5.42 (CH ₂ , 1H), 4.06 (CH , 1H), 2.33 (CH ₃ , 3H), 1.88 (CH, 1H), 1.45 (CH ₂ , 2H), 1.21 (CH ₃ , 3H), 1.19 (CH ₂ , 2H), 1.15 (CH ₂ , 2H) , 0.96 (CH ₃ , 3H)

Example 3-3 Synthesis of Monomer Represented by Chemical Formula 3c

2-methyl-acrylic acid 2-hydroxy-2-methyl-cycloester 2-methyl-acrylic acid 2-hydroxy-5-isopropyl-2- obtained in Example 2-3 instead of 19.8 g (0.10 mol) Except for using 24.0 g (0.10 mol) of methyl-cycloester, 25.6 g of a compound represented by the following Chemical Formula 3c was obtained in the same manner as in Example 3-1 (yield 65%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.80 (CH, 2H), 7.38 (CH, 2H), 6.04 (CH ₂ , 1H), 5.39 (CH ₂ , 1H), 4.12 (CH , 1H), 2.32 (CH ₃ , 3H), 1.84 (CH, 1H), 1.56 (CH ₂ , 2H), 1.49 (CH ₂ , 2H), 1.36 (CH, 1H), 1.35 (CH ₂ , 2H), 1.27 (CH ₃ , 3H), 0.92 (CH ₃ , 6H)

Example 3-4 Synthesis of Monomer Expressed by Chemical Formula 3d

2-methyl-acrylic acid 2-hydroxy-2-methyl-cycloester 2-methyl-acrylic acid 5-acetyl-2-hydroxy-2- obtained in Example 2-4 instead of 19.8 g (0.10 mol) Except for using 24.0 g (0.10 mol) of methyl-cycloester, 24.0 g of a compound represented by the following Chemical Formula 3d was obtained in the same manner as in Example 3-1 (yield 61%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.78 (CH, 2H), 7.41 (CH, 2H), 6.09 (CH ₂ , 1H), 5.45 (CH ₂ , 1H), 4.08 (CH , 1H), 2.36 (CH ₃ , 3H), 2.24 (CH ₃ , 3H), 1.93 (CH ₃ , 3H), 1.71 (CH ₂ , 2H), 1.59 (CH ₂ , 2H), 1.56 (CH ₂ , 2H ), 1.27 (CH ₃ , 3H)

Example 3-5 Synthesis of Monomer Represented by Formula 3e

2-methyl-acrylic acid 2-hydroxy-2-methyl-cyclo ester 2-methyl-acrylic acid 2-cyclohexyl-2-hydroxy ethyl ester obtained in Example 2-5 instead of 19.8 g (0.10 mol) Except that g (0.10 mol) was used, 27.5 g of a compound represented by the following Chemical Formula 3e was obtained in the same manner as in Example 3-1 (yield 75%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.80 (CH, 2H), 7.42 (CH, 2H), 6.04 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 4.14 (CH , 1H), 2.59 (CH, 1H), 2.49 (CH, 1H), 2.31 (CH ₃ , 3H), 1.78 (CH, 1H), 1.21 (CH ₂ , 4H), 1.06 (CH ₂ , 4H), 0.97 (CH ₂ , 2H)

Example 3-6 Synthesis of Monomer Expressed by Chemical Formula 3f

2-methyl-acrylic acid 2-hydroxy-2-methyl-cyclo ester 2-methyl-acrylic acid 2-cyclohexyl-2-hydroxy propyl ester 22.6 obtained in Example 2-6 instead of 19.8 g (0.10 mol) Except for using g (0.10 mol), 27.0g of a compound represented by the following formula (3f) was obtained by the same method as Example 3-1 (yield 71%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.82 (CH, 2H), 7.39 (CH, 2H), 6.06 (CH ₂ , 1H), 5.45 (CH ₂ , 1H), 4.16 (CH , 1H), 2.35 (CH ₃ , 3H), 2.31 (CH, 1H), 1.78 (CH, 1H), 1.32 (CH ₃ , 3H), 1.18 (CH ₂ , 4H), 1.12 (CH ₂ , 4H), 0.99 (CH ₂ , 2H)

Example 3-7 Synthesis of Monomer Expressed by Chemical Formula 3g

2-methyl-acrylic acid 2-hydroxy-2methyl-cyclo ester 2-methyl-acrylic acid 2-cyclohexyl-3-hydroxy-3,7 obtained in Example 2-7 instead of 19.8 g (0.10 mol) 23.9 g of a compound represented by the following formula (3g) was obtained by the same method as Example 3-1, except that 23.8 g (0.10 mol) of, 7-trimethyl-bicyclo [4.1.0] hept-2-yl ester was used. (Yield 61%). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.81 (CH, 2H), 7.35 (CH, 2H), 6.08 (CH ₂ , 1H), 5.45 (CH ₂ , 1H), 4.08 ( CH, 1H), 2.38 (CH ₃ , 3H), 1.72 (CH, 1H), 1.56 (CH ₂ , 2H), 1.38 (CH, 1H), 1.22 (CH ₃ , 3H), 1.18 (CH ₂ , 2H) , 0.98 (CH ₃ , 6H)

Example 3-8 Synthesis of Monomer Expressed by Chemical Formula 3h

2-methyl-acrylic acid 2-hydroxy-2methyl-cycloester 2-methyl-acrylic acid 2-hydroxy-2,6,6-trimethyl obtained in Example 2-8 instead of 19.8 g (0.10 mol) 22.0 g of a compound represented by the following Chemical Formula 3h was obtained by the same method as Example 3-1 except for using 23.8 g (0.10 mol) of -bicyclo [3.1.1] hept-3-yl ester (yield 56%) ). ¹ H-NMR (CDCl ₃ , internal standard): δ (ppm) 7.82 (CH, 2H), 7.38 (CH, 2H), 6.09 (CH ₂ , 1H), 5.49 (CH ₂ , 1H), 4.10 (CH , 1H), 2.36 (CH ₃ , 3H), 1.88 (CH, 1H), 1.74 (CH, 1H), 1.61 (CH, 1H), 1.55 (CH ₂ , 2H), 1.25 (CH ₃ , 3H), 0.99 (CH ₃ , 6H)

Example 4-1 Preparation of Polymer Represented by Chemical Formula 4a

3.52 g (0.01 mol) of monomer represented by Chemical Formula 3a, 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate, 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane and azobis (isobutyronitrile) (AIBN ) 0.7 g was added, the reaction was dissolved in 100 g of anhydrous THF, the gas was removed using an ampoule by a freezing method, and the gas-free reaction was polymerized at 68 ° C. for 24 hours. After the polymerization was completed, the reactant was slowly added dropwise to an excess of diethyl ether, followed by precipitation with THF. The dissolved reactant was reprecipitated in diethyl ether to give 29.1 g of the polymer represented by Formula 4a. Yield 61% {GPC analysis: Mn = 5,538, Mw = 10,024, PD = 1.81}.

[Formula 4a]

Example 4-2 Preparation of a Polymer Represented by Chemical Formula 4b

3.66 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 26.3 g of the polymer represented by Chemical Formula 4b was obtained in a yield of 55% {GPC analysis: Mn = 5,294, Mw = 9,530, PD = 1.80}.

[Formula 4b]

Example 4-3 Preparation of the Polymer Represented by Chemical Formula 4c

3.94 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 23.6 g of the polymer represented by Chemical Formula 4c was obtained in a yield of 49% {GPC analysis: Mn = 4,616, Mw = 8,956, PD = 1.94}.

[Formula 4c]

Example 4-4 Preparation of a Polymer Represented by Chemical Formula 4d

3.94 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 25.0 g of the polymer represented by Chemical Formula 4d was obtained in a yield of 52% {GPC analysis: Mn = 4,677, Mw = 8,792, PD = 1.88}.

[Formula 4d]

Example 4-5 Preparation of the Polymer Represented by Chemical Formula 4e

3.66 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 25.3 g of the polymer represented by Chemical Formula 4e was obtained in a yield of 53% {GPC analysis: Mn = 5,085, Mw = 9,458, PD = 1.86}.

[Formula 4e]

Example 4-6 Preparation of a Polymer Represented by Chemical Formula 4f

3.80 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 26.4 g of the polymer represented by Chemical Formula 4f was obtained in a yield of 55% {GPC analysis: Mn = 5,674, Mw = 9,930, PD = 1.75}.

[Formula 4f]

Example 4-7 Preparation of the Polymer Represented by Chemical Formula 4g

3.92 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 23.1 g of the polymer represented by Chemical Formula 4 g was obtained in a yield of 48% {GPC analysis: Mn = 5,299, Mw = 9,485, PD = 1.79}.

[Formula 4g]

Example 4-8 Preparation of the Polymer Represented by Chemical Formula 4h

3.92 g (0.01 mol) and 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one 8.89 g (0.04 mol), 2- Example 4-1 except that 23.4 g (0.1 mol) of methyl-2-adamantyl methacrylate and 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane were used In the same manner, 23.6 g of the polymer represented by Chemical Formula 4h was obtained in a yield of 49% {GPC analysis: Mn = 4,382, Mw = 8,239, PD = 1.88}.

[Formula 4h]

[Comparative Example 4] Preparation of the polymer represented by the following formula (5)

8.89 g (0.04 mol) of 9-methacryloyl oxy-4-oxa-tricyclo [5.2.1.0 ^2,6 ] decane-3-one, 23.4 g (2-methyl-2-adamantyl methacrylate) mol), except that 11.8 g (0.05 mol) of 1-methacryloyl oxy-3-hydroxy adamantane was used, the polymer represented by the following Chemical Formula 5 was obtained in the same manner as in Example 4-1 {GPC Analyzes: Mn = 5,124, Mw = 9,201, PD = 1.80}.

Example 5 Preparation and Pattern Formation of Photoresist Composition

2 g of the polymers prepared in Examples 4-1 to 4-8 and Comparative Example 4 were filtered together with 0.02 g of triphenyl sulfonium triflate, respectively (Examples 5-1 to 5-7, Comparative Examples). 5) was obtained.

Each obtained photoresist composition was spin-coated on the etching target layer of the silicon wafer to prepare a photoresist thin film, followed by soft baking for 90 seconds in an oven or hot plate at 90 ° C., and then exposed to light using an ArF laser exposure apparatus, followed by 90 ° at 130 ° C. Bake again for a second. The baked wafer was immersed in a 2.38 wt% TMAH aqueous solution for 40 seconds and developed to form a L / S pattern of 0.07 mu m. The performance comparison including the photo speed of the photoresist composition is shown in Table 1, and the depth of focus and the photo speed (EOP) are collectively shown in FIGS. 1 and 2.

TABLE 1

As described above, the secondary acid may be generated due to decomposition of the sulfonyl group included in the main chain of the polymer as well as generation of acid by exposure through a baking process after the lithography process according to the present invention. The generation of the secondary acid has an advantage of improving the resolution and process margin of the photoresist pattern, the depth of focus margin and the line edge roughness of the photoresist layer, as compared with the conventional photoresist. In addition, since the photoresist polymer and the photoresist composition including the same have high dry etching stability and post-exposure bake temperature stability, an accurate pattern may be realized.

Claims (6)

An acrylic photoresist monomer comprising a sulfonyl group represented by the following formula (1). [Formula 1]

or

In Formula 1, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, phenyl group, benzyl group, toluene group, xylene group, perfluoromethyl group, perfluoroethyl group, Perfluoropropyl group, perfluoro butyl group, and perfluorooctyl group. delete A photoresist polymer represented by the following formula (4). [Formula 4]

or

In Formula 4, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, phenyl group, benzyl group, toluene group, xylene group, perfluoromethyl group, perfluoroethyl group, Perfluoropropyl group, perfluoro butyl group, and perfluorooctyl group; a, b, c and d are mol% of the repeating unit which comprises the said polymer, and are each independently 1-95 mol%. The photoresist polymer of claim 3, wherein the photoresist polymer is selected from the group represented by the following Chemical Formulas 4a to 4h. [Formula 4a]

[Formula 4b]

[Formula 4c]

[Formula 4d]

[Formula 4e]

[Formula 4f]

[Formula 4g]

[Formula 4h]

In Formulas 4a to 4h, R ^* , a, b, c, and d are as defined in Formula 4. A photoresist polymer comprising a monomer represented by the formula (1), [Formula 1]

or

In Formula 1, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, phenyl group, benzyl group, toluene group, xylene group, perfluoromethyl group, perfluoroethyl group, Perfluoropropyl group, perfluoro butyl group and perfluorooctyl group; Photoacid generators generating acid; Organic solvents, With respect to 100 parts by weight of the photoresist polymer, the content of the photoacid generator is 0.1 to 20 parts by weight, the content of the organic solvent is 300 to 5000 parts by weight. a) a photoresist polymer comprising a monomer represented by Formula 1 below ; Photoacid generators generating acid; And applying a photoresist composition comprising an organic solvent on the etched layer to form a photoresist film. [Formula 1]

or

In Formula 1, R ^* and R ^' are each independently hydrogen or a methyl group; R, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, an alkyl or ketone group having 1 to 20 carbon atoms, a cycloalkyl group or a multicycloalkyl group having 4 to 20 carbon atoms; R ₅ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, hexyl group, phenyl group, benzyl group, toluene group, xylene group, perfluoromethyl group, perfluoroethyl group, Perfluoropropyl group, perfluoro butyl group and perfluorooctyl group; b) exposing the photoresist film in a predetermined pattern; c) heating the exposed photoresist film; And d) developing the heated photoresist film to obtain a desired pattern.

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