KR101259853B1 - Photosensitive Polymer and photoresist composition including the same - Google Patents

Abstract

Disclosed are a photosensitive polymer polymerized using a monomer represented by the following formula and a photoresist composition comprising the same. The photosensitive polymer and the photoresist composition may improve the resolution, process margin, line edge roughness, etc. by generating a base capable of controlling acid diffusion in the exposure part, and have low PEB sensitivity after exposure. Therefore, a precise pattern can be realized.

In the above formula, R ^* is hydrogen or methyl, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono- or multi-cyclic homo or hetero saturated hydrocarbon group having 3 to 50 carbon atoms R ₂ and R ₃ are each independently a chain or a cyclic alkyl group having 1 to 30 carbon atoms which combine with each other to form a heterocyclic compound.

Photosensitive Polymer, Photoresist, Line Edge Roughness

Description

Photosensitive polymer and photoresist composition comprising same {Photosensitive Polymer and photoresist composition including the same}

1 to 4 are electron scanning micrographs of photoresist patterns each formed using a photoresist composition according to one embodiment of the present invention.

The present invention relates to a photosensitive polymer and a photoresist composition comprising the same, and more particularly, a carbamoyl group generates a base capable of controlling acid diffusion in an exposed portion, thereby providing resolution, process flexibility, and line edge roughness. The present invention relates to a photosensitive polymer and a photoresist composition including the same, which may improve the quality thereof and may implement a precise pattern because of low post-exposure bake temperature sensitivity.

In recent years, with the high integration of semiconductor devices, development of dynamic random access memory (DRAM) having a storage capacity of more than a gigabit level has been actively progressed. In order to manufacture DRAM of 1 gigabit or more, an ultrafine pattern having a line width of 100 nm or less must be formed. To this end, photolithography technology using a short wavelength exposure source such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) has been introduced, and not only has high resolution in short wavelength exposure sources, but also transparency and dry etching. Research into photoresist compositions excellent in resistance, adhesion to lower film quality, and developability is being actively conducted. In particular, as the pattern becomes finer, the photo and etching process margins must be reduced, thereby improving the transparency of the resist composition, reducing line edge roughness, and decreasing line width variations due to post exposure bake (PEB) temperature. The importance of the back is increasing.

In general, the positive chemically amplified photoresist includes a photoacid generator (PAG) that generates an acid component by exposure and a photosensitive polymer having a protecting group decomposed by the acid component. When the chemically amplified photoresist is exposed, an acid component is generated from the photoacid generator, and the generated acid component serially decomposes the protecting group bonded to the skeleton of the polymer to change the solubility of the polymer. It will form a pattern with a high contrast (contrast). In the photolithography process using such chemically amplified photoresist, line edge roughness (LER) and post-exposure bake temperature sensitivity (PEB sensitivity) corresponding to noise of the polymer resist are important factors for determining the profile of the shaped pattern. admit. This line edge roughness (LER) and post-exposure bake temperature sensitivity can be improved by adjusting the acid diffusion of the exposed portion. Acid diffusion can be controlled by an acid diffusion regulator added from the outside, amine base is widely used as acid diffusion regulator. However, the use of the amine base acid diffusion regulator has a problem of inefficiently performing acid diffusion control as the regulator is diffused. In other words, the amount of photo-acid generated in the exposed portion becomes smaller from the resist surface to the substrate film quality, and the difference in acid diffusion resulting from this results in a non-uniform exposure pattern.

Accordingly, an object of the present invention is to generate an acid diffusion regulator to produce a photosensitive resist that meets the requirements of the exposure technique, to improve the resolution and process margin, and to produce a precise pattern because the baking temperature is low after exposure. It is to provide a photosensitive polymer that can be implemented and a photoresist composition comprising the same.

It is another object of the present invention to provide a photoresist polymer and a photoresist composition comprising the same, which can improve dry etching resistance, depth of focus margin and line edge roughness.

Still another object of the present invention is to provide a monomer of the photosensitive polymer, a method of manufacturing the same, and a method of forming a photoresist pattern using the photoresist composition.

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

[Formula 1]

In Formula 1, R ^* is hydrogen or a methyl group, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono-cyclic or multi-cyclic homo or hetero saturated hydrocarbon having 3 to 50 carbon atoms And R ₂ and R ₃ are each independently a chain or a cyclic alkyl group having 1 to 30 carbon atoms which combine with each other to form a heterocyclic compound.

In another aspect, the present invention provides a photosensitive polymer comprising a repeating unit represented by the following formula (2).

 [Formula 2]

In Formula 2, R ^* , R ₁ , R ₂ and R ₃ are as defined in Formula 1.

The present invention also provides a photoresist composition comprising the photosensitive polymer and a method of forming a photoresist pattern using the photoresist composition.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The monomer of the photosensitive polymer according to the present invention is represented by the following formula (1).

In Formula 1, R ^* is hydrogen or a methyl group, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono-cyclic or multi-cyclic homo or hetero saturated hydrocarbon having 3 to 50 carbon atoms And R ₂ and R ₃ are each independently a chain or a cyclic alkyl group having 1 to 30 carbon atoms which combine with each other to form a heterocyclic compound.

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등이며, 점선 표시는 결합위치를 나타낸다. 상기 R₂ 및 R₃가 서로 결합하여 고리화합물을 형성하는 경우, 카바모일기의 질소원자(N)를 함유한

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등의 헤테로고리화합물을 형성할 수 있다.Preferred examples of R ₁

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And the dotted line indicates the engagement position. When R ₂ and R ₃ are bonded to each other to form a cyclic compound, it contains a nitrogen atom (N) of the carbamoyl group

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Heterocyclic compounds, such as these can be formed.

The monomer represented by Formula 1 according to the present invention may be prepared by a conventional organic synthesis method. For example, as shown in Scheme 1 below, hydroxyalkyl (meth) acrylate and carbamoyl chloride are prepared by reacting under a base catalyst.

In Scheme 1, R ^* , R ₁ , R ₂ and R ₃ are as defined in the formula (1).

The base catalyst can be used a wide range of commonly used base catalyst, for example triethylamine can be used. The reaction may be carried out in a conventionally used organic solvent such as tetrahydrofuran in a nitrogen or argon atmosphere for 1 to 24 hours at a temperature of 30 to 100 ℃ and atmospheric pressure.

The present invention provides a photosensitive polymer comprising a repeating unit represented by the following Chemical Formula 2.

In Formula 2, R ^* , R ₁ , R ₂ and R ₃ are as defined in Formula 1.

In addition, a preferred example of the photosensitive polymer according to the present invention is represented by the following formula (3), more preferably a photosensitive polymer represented by the formula (3a to 3h).

In Formula 3, R ^* , R ₁ , R ₂ and R ₃ are as defined in Formula 1, R is a mono-cyclic or poly-cyclic hydrocarbon having 3 to 50 carbon atoms , a, b are mol% of the repeating units to the total repeating units constituting the photosensitive polymer, each independently 0.01 to 50 mol%, 50 to 99.99 mol%.

In Formulas 3a to 3h, a and b are the same as defined in Formula 3.

According to the present invention, the photosensitive polymer and the photoresist composition generate a base capable of controlling acid diffusion in the exposure part, thereby controlling the imbalance of acid diffusion due to the difference in the intensity of the light source according to the aerial image. In addition, the process margin, line edge roughness, and the like can be improved, and since the post-exposure bake temperature sensitivity (PEB sensitivity) is low, a precise pattern can be realized.

Preparation of the photosensitive polymer according to the present invention comprises a) dissolving the monomer represented by Formula 1 and the monomer represented by Formula 4 in a polymerization solvent, b) adding a polymerization initiator to the mixture solution, c) The added mixture solution may be prepared by reacting at 60 to 70 ° C. for 4 to 24 hours under an inert atmosphere such as nitrogen and argon. Preferably, the polymerization may be performed by a radical polymerization reaction, a solution polymerization reaction, a bulk polymerization reaction or a polymerization reaction using a metal catalyst. In addition, the preparation method may include the step of crystallizing the reaction product (c) using diethyl ether, petroleum ether, lower alcohols including methanol, ethanol or isopropanol, water, mixtures thereof, and the like. It may be.

In Formula 4, R ^* and R are as defined in Formula 3.

The monomer represented by Formula 1 and the monomer represented by Formula 4 may be polymerized as in Scheme 2 to produce a photosensitive polymer represented by Formula 3.

As the polymerization solvent of the polymerization reaction, a polymerization solvent commonly known in the art may be widely used, but is not limited to cyclohexanone, cyclopentanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, dioxane, Methyl ethyl ketone, benzene, toluene, xylene, or mixtures thereof may be exemplified, and the polymerization initiator may also be widely used as polymerization initiators commonly known in the art, but is not limited to benzoyl peroxide, 2, 2'-azobisisobutyronitrile (AIBN), acetylperoxide, lauryl peroxide, t-butylperacetate, t-butylhydroperoxide, di-t-butylperoxide or mixtures thereof have. The photosensitive polymer of Chemical Formulas 2 to 3 preferably have a weight average molecular weight of 3,000 to 100,000 and a degree of dispersion of 1.0 to 5.0. When the weight average molecular weight and the dispersion degree are outside the above ranges, the physical properties of the photoresist film may be reduced, or the formation of the photoresist film may be difficult, and the contrast of the pattern may be lowered.

 The photoresist composition according to the present invention includes a photosensitive polymer including a repeating unit represented by Chemical Formula 2, a photoacid generator for generating an acid and an organic solvent, and may further include various additives as necessary. The content of the photosensitive polymer including the repeating unit represented by Formula 2 is preferably 1 to 30% by weight based on the total photoresist composition, more preferably 5 to 15% by weight. If the content of the photosensitive polymer is less than 1% by weight, the resist layer remaining after coating is too thin to form a pattern having a desired thickness, and if it exceeds 30% by weight, coating uniformity may be degraded.

The photoacid generator generates an acid component such as H ⁺ by exposure and induces chemical amplification, and may be any compound which can generate an acid by light, and preferably a sulfide salt such as eutechonic acid. Onium salt type compounds, such as a type | system | group compound and an onium salt, and mixtures thereof can be used. Non-limiting examples of photoacid generators include phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, nap having low absorbance at 157 nm and 193 nm. Naphthylimido trifluoromethane sulfonate, diphenyluredo hexafluorophosphate, diphenyluredo salt hexafluoro arsenate, diphenyluredo salt hexafluoro antimonate, diphenylparamethoxyphenylsulfonium Triflate, Diphenylparatoluenylsulfonium Triflate, Diphenylparaisobutylphenylsulfonium Triflate, Triphenylsulfonium Hexafluoro Arsenate, Triphenylsulfonium Hexafluoro Antimonate, Triphenylsulfonium Triflate, dibutylnaphthylsulfonium triflate, and mixtures thereof. The content of the photoacid generator is preferably 0.05 to 10% by weight based on the photosensitive polymer. If less than 0.05% by weight, the sensitivity of the photoresist composition to light is reduced, which may make it difficult to deprotect the protective group. If it exceeds 10% by weight, a large amount of acid may be generated in the photoacid generator, resulting in poor cross-section of the resist pattern. There is concern.

As the organic solvent constituting the remaining components of 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 ether, ethylene glycol Monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol, propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, Methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate, ethyl ethoxy propionate, N, N-dimethylformamide , N, N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxye Propionate, 2-heptanone, gamma-butyrolactone, 2-hydroxypropionethyl, 2-hydroxyethyl 2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy 3-methylpart Methyl carbonate, 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate, ethyl acetate, butyl acetate and mixtures thereof.

In addition, the photoresist composition according to the present invention may further include an organic base as needed, non-limiting examples of the organic base is triethylamine, triisobutylamine, triisooctylamine, diethanolamine, triethanol Amines and mixtures thereof can be exemplified. The content of the organic base is preferably 0.01 to 2.00% by weight based on the total photoresist composition. When the content of the organic base is less than 0.01% by weight, a t-top phenomenon may occur in the resist pattern, and when the content exceeds 2.00% by weight, the sensitivity of the photoresist composition may be lowered, thereby lowering the process progress rate.

The photoresist composition according to the present invention may be prepared by blending the photosensitive polymer, photoacid generator, organic solvent and various additives as necessary, and filtering by a filter as necessary, wherein, based on 100 parts by weight of the total photoresist It is preferable to make solid content concentration into 10 to 60 weight%. When the concentration of the solid content is less than 10% by weight, the resist layer remaining after coating is too thin to form a pattern having a desired thickness, and when it exceeds 60% by weight, coating uniformity may be degraded.

In order to form a photoresist pattern using the photoresist composition according to the present invention, first, the photoresist composition is applied to a substrate such as a silicon wafer or an aluminum substrate using a spin coater to form a photoresist film. After exposing the photoresist film to a predetermined pattern, and then forming the photoresist pattern by a conventional photolithography process in which the exposed photoresist pattern is exposed and heated after exposure and developed, a semiconductor device having a desired pattern can be provided. As the 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. Accordingly, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added to the developer. In addition, after the development process, the cleaning process may be further performed to clean the substrate 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 scope of the present invention is not limited by the following examples.

Example 1-1 Preparation of Monomers Represented by Formula 5a

 In a 500 mL three-necked round bottom flask, 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate was dissolved in 60 g of tetrahydrofuran, and 10 mL of triethylamine was added thereto. Next, a mixture of 10.8 g (0.1 mol) of dimethylcarbamoyl chloride and 50 g of tetrahydrofuran (THF) was added using a dropping funnel, and then refluxed in a nitrogen atmosphere for 12 hours. After the reaction was completed, the solvent was removed under reduced pressure, the reaction mixture was separated by liquid chromatography (silica gel, hexane: ether = 6: 1), and the solvent was removed again. After the solvent was removed, the reaction product was recrystallized with hexane and left at room temperature to obtain a monomer represented by the following Chemical Formula 5a in a yield of 60%. {H-NMR: m (6.15, 1H), m (5.58, 1H), m (4.4, 4H), s (2.9, 6H), s (1.9, 3H)}.

Example 1-2 Preparation of Monomer Represented by Formula 5b

The monomer represented by the following Chemical Formula 5b was obtained in the same manner as in Example 1-1 except that 16.4 g of diisopropylcarbamoyl chloride was used instead of 10.8 g (0.1 mol) of dimethyl carbamoyl chloride in a yield of 55%. H-NMR: m (6.15, 1H), m (5.58, 1H), m (4.4, 4H), m (3.9, 2H), s (1.9, 3H), d (1.3, 12H)}.

Example 1-3 Preparation of Monomer Represented by Formula 5c

Except for using 13.4 g of 1-pyrrolidine carbonyl chloride instead of 10.8 g (0.1 mol) of dimethylcarbamoyl chloride, the monomer represented by the following Chemical Formula 5c was obtained in a yield of 65% in the same manner as in Example 1-1. H-NMR: m (6.15, 1H), m (5.58, 1H), m (4.4, 4H), t (3.3, 4H), s (1.9, 3H), t (1.6, 4H)}.

Example 1-4 Preparation of Monomers Represented by Formula 5d

Except for using 14.8 g of 1-piperidylcarbonyl chloride instead of 10.8 g (0.1 mol) of dimethylcarbamoyl chloride, the monomer represented by the following Chemical Formula 5d was produced in the same manner as in Example 1-1 in 60% yield. {H-NMR: m (6.15, 1H), m (5.58, 1H), m (4.4, 4H), t (3.3, 4H), s (1.9, 3H), m (1.45, 6H)}.

Example 1-5 Preparation of a Monomer Represented by Formula 5e

Except for using 2hydroxyg (0.1 mole) of 3-hydroxyadamantyl methacrylate instead of 13.0 g (0.1 mole) of 2-hydroxyethyl methacrylate in the same manner as in Example 1-1 The monomer represented by was obtained in 45% yield {H-NMR: m (6.15, 1H), m (5.58, 1H), s (2.9, 6H), s (1.9, 3H), m (1.3, 14H) }.

Example 1-6 Preparation of a Monomer Represented by Formula 5f

Formula 5f in the same manner as in Example 1-2, except that 23.6 g (0.1 mol) of 3-hydroxyadamantyl methacrylate was used instead of 13.0 g (0.1 mol) of 2-hydroxyethylmethacrylate. The monomer represented by was obtained in 40% yield {H-NMR: m (6.15, 1H), m (5.58, 1H), s (3.9, 2H), s (1.9, 3H), m (1.4, 26H) }.

[Example 1-7] Preparation of monomer represented by the following chemical formula 5g

5 g of the following Chemical Formula 5 in the same manner as in Example 1-3, except that 23.6 g (0.1 mol) of 3-hydroxyadamantyl methacrylate was used instead of 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate The monomer represented by was obtained in a yield of 45% {H-NMR: m (6.15, 1H), m (5.58, 1H), t (3.3, 4H), s (1.9, 3H), m (1.4, 18H) }.

[Example 1-8] Preparation of the monomer represented by the following formula (5h)

Formula 5h in the same manner as in Example 1-4, except that 23.6 g (0.1 mol) of 3-hydroxyadamantyl methacrylate was used instead of 13.0 g (0.1 mol) of 2-hydroxyethyl methacrylate The monomer represented by was obtained in a yield of 45% {H-NMR: m (6.15, 1H), m (5.58, 1H), t (3.3, 4H), s (1.9, 3H), m (1.4, 20H) }.

Example 2-1 Preparation of Photosensitive Polymer Represented by Formula 3a

20.1 g (0.1 mol) of monomers represented by Formula 5a, 22.2 g (0.1 mol) of methyladamantyl methacrylate, and azobis (isobutyronitrile) (AIBN) prepared in Example 1-1 in a reactor 0.7 g was added, the reactant was dissolved in 25 g of anhydrous THF, and gas was removed using an ampoule by freezing. The gas-free reaction was polymerized at 68 ° C. for 24 hours. After the polymerization reaction 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 a photosensitive polymer represented by Chemical Formula 3a. Prepared in% yield {GPC analysis: Mw = 8912, PD = 1.80}.

Example 2-2 Preparation of Photosensitive Polymer Represented by Chemical Formula 3b

The same method as in Example 2-1, except that 25.7 g (0.1 mole) of the monomer represented by Formula 5b prepared in Example 1-2 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3b was prepared in a yield of 63% {GPC analysis: Mw = 9316, PD = 1.87}.

Example 2-3 Preparation of Photosensitive Polymer Represented by Formula 3c

The same method as in Example 2-1, except that 22.7 g (0.1 mole) of the monomer represented by Formula 5c prepared in Examples 1-3 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3c was prepared in a yield of 55% {GPC analysis: Mw = 8653, PD = 1.79}.

Example 2-4 Preparation of Photosensitive Polymer Represented by Chemical Formula 3d

The same method as Example 2-1 except for using 24.1 g (0.1 mole) of the monomer represented by Formula 5d prepared in Example 1-3 instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a The photosensitive polymer represented by Chemical Formula 3d was prepared in a yield of 60% {GPC analysis: Mw = 8998, PD = 1.88}.

Example 2-5 Preparation of Photosensitive Polymer Represented by Formula 3e

The same method as in Example 2-1, except that 30.7 g (0.1 mole) of the monomer represented by Formula 5e prepared in Example 1-3 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3e was prepared in a yield of 55% {GPC analysis: Mw = 9252, PD = 1.89}.

Example 2-6 Preparation of Photosensitive Polymer Represented by Formula 3f

The same method as in Example 2-1, except that 36.3 g (0.1 mole) of the monomer represented by Formula 5f prepared in Example 1-3 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3f was prepared in a yield of 60% {GPC analysis: Mw = 9762, PD = 1.83}.

Example 2-7 Preparation of Photosensitive Polymer Represented by Chemical Formula 3g

The same method as in Example 2-1, except that 33.3 g (0.1 mole) of the monomer represented by Formula 5 g prepared in Example 1-3 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3g was prepared in a yield of 55% {GPC analysis: Mw = 9248, PD = 1.86}.

Example 2-8 Preparation of Photosensitive Polymer Represented by Formula 3h

The same method as in Example 2-1, except that 34.7 g (0.1 mole) of the monomer represented by Formula 5h prepared in Example 1-3 was used instead of 20.1 g (0.1 mole) of monomer represented by Formula 5a. The photosensitive polymer represented by Chemical Formula 3h was prepared in a yield of 65% {GPC analysis: Mw = 9532, PD = 1.97}.

[Examples 3-1 to 3-8] Preparation of a photoresist composition containing the photosensitive polymer prepared in Examples 2-1 to 2-8

2 g of the photosensitive polymer prepared in Example 2-1, 0.024 g of phthalimidotrifluoromethanesulfonate and 0.06 g of triphenylsulfonium triflate (TPS-105) were dissolved in 20 g of propylene glycol monomethyl ether acetate (PGMEA). Thereafter, a photoresist composition was prepared by filtration with a 0.20 μm filter, except that 2 g of the photosensitive polymer prepared in Examples 2-2 to 2-8 was used instead of 2 g of the photosensitive polymer prepared in Example 2-1. Prepared a photoresist composition in the same manner.

[Examples 4-1 to 4-8] Exposure pattern formation using photoresist composition

After spin coating the photoresist compositions prepared in Examples 3-1 to 3-8 on the etched layer of the silicon wafer to prepare a photoresist thin film, soft bake for 90 seconds in an oven or hot plate at 90 ° C., and ArF After exposure with a laser exposure equipment, it was heated again at 120 ° C. for 90 seconds. The heated wafer was immersed in a 2.38 wt% TMAH aqueous solution for 40 seconds to develop, thereby forming a L / S pattern of 0.07 μm. Physical properties of the formed photoresist pattern are shown in Table 1 below, and electron scanning micrographs of the photoresist patterns formed using the compositions prepared in Examples 3-5 to 3-8 are shown in FIGS. 1 to 4, respectively. .

Resist
Composition Minimum resolution
[Mu m] Depth of focus
[Mu m] Line Edge Roughness [nm] energy
Fair margin [%] Post-exposure bake
Temperature Stability [nm / ℃] pattern
profile 3-1 0.06 0.40 5.5 12.0 2 Great 3-2 0.06 0.35 5.5 12.5 3 Great 3-3 0.06 0.35 4.7 15.0 One Great 3-4 0.06 0.40 4.5 13.0 2 Very good 3-5 0.06 0.45 5.5 13.5 3 Very good 3-6 0.06 0.45 6.5 10 2.5 Great 3-7 0.06 0.35 5.4 12 2.5 Very good 3-8 0.06 0.40 5.5 12 3 Great

From Table 1, the photoresist composition comprising the photosensitive polymer of the present invention exhibits a minimum resolution of 0.06 micrometers (µm), an energy process margin of 10% or more, a depth of focus of 0.35 micrometers (µm) or more, and line edge roughness. (LER) shows excellent performance of less than 6.5 nanometers (nm) and stable post-exposure bake temperature sensitivity (PEB sensitivity) of less than 3 nanometers (nm), especially minimizing the change in pattern profile by acid diffusion It shows excellent.

The photosensitive polymer according to the present invention and the photoresist composition comprising the same have the advantage that the carbamoyl group generates an acid diffusion regulator, thereby improving the resolution and process margin of the resist pattern, and also having high dry etching stability and stability. Since the baking temperature stability after exposure has the advantage that it is possible to implement a precise pattern. In addition, the photosensitive polymer and the photoresist composition including the same have an advantage of improving the depth of focus margin and line edge roughness of the resist film.

Claims (11)

delete delete delete delete The photosensitive polymer represented by the following formula (3). (3)

In Formula 3, R ^* is hydrogen or a methyl group, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono-cyclic or multi-cyclic homo or hetero saturated hydrocarbon having 3 to 50 carbon atoms. R ₂ and R ₃ are each independently present or are a chain or cyclic alkyl group having 1 to 30 carbon atoms to combine with each other to form a heterocyclic compound, R is a mono-cyclic (C3-C50) Or a polycyclic hydrocarbon, and a and b are mol% of the repeating units with respect to the total repeating units constituting the photosensitive polymer, and are each independently 0.01 to 50 mol% and 50 to 99.99 mol%. . The photosensitive polymer of claim 5, wherein the photosensitive polymer is selected from the group represented by the following Chemical Formulas 3a to 3h. [Chemical Formula 3]

(3b)

[Formula 3c]

[Formula 3d]

[Formula 3e]

[Formula 3f]

[Formula 3g]

[Formula 3h]

In Formulas 3a to 3h, a and b are mol% of the repeating units with respect to all the repeating units constituting the photosensitive polymer, and are each independently 0.01 to 50 mol% and 50 to 99.99 mol%. A polymer comprising a repeating unit represented by the formula (2) [Formula 2]

In Formula 2, R ^* is hydrogen or a methyl group, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono-cyclic or multi-cyclic homo or hetero saturated hydrocarbon having 3 to 50 carbon atoms R ₂ and R ₃ are each independently a chain or a cyclic alkyl group having 1 to 30 carbon atoms which combine with each other to form a heterocyclic compound; Photoacid generators generating acid; And Photoresist composition comprising an organic solvent. The photoresist composition of claim 7, wherein the photoresist composition comprises 1 to 30 wt% of the polymer based on the total photoresist composition, 0.05 to 10 wt% of the photoacid generator based on the polymer, and the remaining organic solvent. The method of claim 7, wherein the photoacid generator is phthalimidotrifluoromethanesulfonate, dinitrobenzyltosylate, n-decyldisulfone, naphthylimidotrifluoromethanesulfonate, diphenyl iodo salt hexafluorophosphate, Diphenylurodoxyl hexafluoro arsenate, diphenylurodoxyl hexafluoro antimonate, diphenylparamethoxyphenylsulfonium triflate, diphenylparatoluenylsulfonium triflate, diphenylparaisobutylphenylsulfonium tri Plate, triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate and mixtures thereof Photoresist composition. The method of claim 7, wherein the organic solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate , Propylene glycol, propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy Propionate, ethylethoxy propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethylpropionate, 2-heptanone, Gamma-butyrolactone, 2-hydroxypropionethyl, 2-hydroxyethyl 2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy 3-methylbutanoic acid Photoresist composition selected from the group consisting of methyl, 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy 2-methylpropionate, ethyl acetate, butyl acetate and mixtures thereof . A photosensitive polymer comprising a repeating unit represented by Formula 2 below; Photoacid generators generating acid; And applying a photoresist composition comprising an organic solvent to the substrate to form a photoresist film, [Formula 2]

In Formula 2, R ^* is hydrogen or a methyl group, R ₁ is an alkylene group having 1 to 30 carbon atoms or a mono-cyclic or multi-cyclic homo or hetero saturated hydrocarbon having 3 to 50 carbon atoms R ₂ and R ₃ are each independently a chain or a cyclic alkyl group having 1 to 30 carbon atoms which combine with each other to form a heterocyclic compound; And Exposing the photoresist film in a predetermined pattern; and then heating and developing the exposed photoresist pattern after exposure.

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