KR20150046613A - Coating composition for forming fine pattern and method for forming fine pattern using the same - Google Patents

Abstract

Disclosed are a coating composition for forming a fine pattern, which can form a negative tone pattern by using an alkali water-soluble positive tone developer; and a method for forming the fine pattern using the same coating composition. The coating composition includes a photosensitive polymer compound including a monomer represented by chemical formula 1 below, a photo-acid generator, an acid diffusion control agent, and an organic solvent. In chemical formula 1, R_1 is a -CH_2CF_3 group or a -CH_2OCH_3 group; R_2 is a linear or branched hydrocarbon or fluorocarbon group which has one to four carbon atoms and includes fluorine (F) or not; R_3 is a linear, branched, or cyclic, and saturated or unsaturated hydrocarbon group of 1-25 carbon atoms, which includes or does not include 1-20 hetero atoms; R_4 is a hydrogen atom or a methyl group; and n is the number of a repeated unit of hydro carbon, and is 0-12.

Description

[0001] The present invention relates to a coating composition for forming a fine pattern and a method for forming a fine pattern using the coating composition.

The present invention relates to a coating composition for forming fine patterns, and more particularly,

A negative tone pattern can be formed using an alkali-soluble positive tone developer, and a method for forming a fine pattern using the coating composition.

As a method of forming a fine pattern, there is a need for development of an exposure apparatus or miniaturization of a pattern through introduction of an additional process (for example, pattern coating process) Reduction of the pattern space through) is most effective. As a photoresist pattern forming method, there are a negative tone developing solution (NTD) and a positive tone developing solution (PTD, Positive Tone Development). The pattern forming method using the negative tone developing solution is to form a pattern by selectively dissolving and removing the non-exposed region with a negative tone developing solution. In the pattern forming method using the positive tone developing solution, by selectively dissolving and removing the exposed region with a positive tone developing solution To form a pattern. The method of forming a pattern using the negative tone developer can realize a reversed phase pattern even in a contact hole pattern or a trench pattern which is difficult to form due to insufficient exposure amount as compared with a pattern forming method using a positive tone developer, And an organic solvent is used as a developer for removing unexposed portions, so that a photoresist pattern can be formed more effectively. However, when the above-mentioned organic solvent is used as a negative tone developer, there is a disadvantage that additional equipment is required. In the conventional negative photoresist (KrF), the solubility is lowered by cross-linking with a linker in the exposed region, and a pattern is realized. As a result, there arises a problem of resolution, and almost no application is found in the ArF photoresist. In addition, when a conventional negative tone development is performed with a resist composition, a protecting group is converted into a carboxyl group (-COOH) by an acid (H ⁺ ), resulting in a disadvantage that etching resistance is weaker than that of an original resist composition (Korean Patent Laid-Open Nos. 10-2013-0009695, 10-2013-0014351, and 10-2010-0075766). Korean Patent Application No. 10-2009-7023570, on the other hand, simplifies the process and improves the etch resistance, but a method of coating a crosslinking material after patterning, which is different from the present invention, is used.

Accordingly, an object of the present invention is to provide a coating composition for forming a fine pattern which can economize not only economic but also simplify the process of negative tone development by using a conventional alkaline water-soluble developer, And a method of forming a pattern.

Another object of the present invention is to provide a coating composition for forming fine patterns capable of improving resolution and etching resistance by using a method of lactonization by deviating from the conventional pattern formation by crosslinking, Method.

In order to achieve the above object, the present invention provides a coating composition for forming a fine pattern, which comprises a photosensitive polymer comprising a monomer represented by the following general formula (1), a photoacid generator, an acid diffusion controller and an organic solvent.

[Chemical Formula 1]

Wherein R ₁ is a -CH ₂ CF ₃ group or a -CH ₂ OCH ₃ group, R ₂ is a linear or branched hydrocarbon group having 1 to 4 carbon atoms, which may or may not contain a fluorine (F) atom, or R ₃ is a linear or branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms, which may or may not contain 1 to 20 heteroatoms, R ₄ is a hydrogen atom or a methyl group, n is the number of repeating units of the hydrocarbon,

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, including: forming a photoresist film by applying a coating composition for forming a fine pattern on a semiconductor substrate having a pattern layer; Exposing the photoresist film with an exposure mask and an exposure apparatus; And developing the resist film with an alkali water-soluble developer, which is a positive tone developer, to form a photoresist pattern.

The coating composition for forming a fine pattern according to the present invention can be used in a conventional alkaline water-soluble developer (for example, tetramethyl ammonium hydroxide (TMAH) or (2-hydroxyethyl) trimethyl ammonium hydroxide) Thus, it is possible to use the developing apparatus used in the pattern formation process without the need of installing an additional developing unit, which is economical and can simplify the negative tone developing process. In addition, by using the coating composition according to the present invention, it is possible to use a method of forming a pattern by reducing the solubility by lactonization, deviating from pattern formation by conventional crosslinking, And the etching resistance can be improved.

Hereinafter, the present invention will be described in detail.

The coating composition for forming a fine pattern according to the present invention is for forming a coating film on a wafer and forming a pattern using a developer. The coating composition for forming a pattern includes a photosensitive polymer compound containing a monomer represented by the following formula (1) , Acid diffusion controllers and organic solvents.

[Chemical Formula 1]

Wherein R ₁ is a -CH ₂ CF ₃ group or a -CH ₂ OCH ₃ group and R ₂ is a group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, with or without a fluorine (F) atom, More preferably a linear or branched hydrocarbon group or fluorocarbon group having 2 to 3 carbon atoms, and R ₃ is a linear, branched and / or cyclic hydrocarbon group having 1 to 25 carbon atoms, which may or may not contain 1 to 20 hetero atoms Branched and / or cyclic hydrocarbon group of 4 to 20 carbon atoms which preferably contains 1 to 10 oxygen atoms and / or nitrogen (N) atoms, and the like. Saturated or unsaturated hydrocarbon group which contains both an acid-labile structure of an acetal protecting group. R ₄ is a hydrogen atom or a methyl group, and n is 0 to 12, preferably 1 to 10, more preferably 1 to 5, as the number of repeating units of the hydrocarbon.

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등이 있다.Specific examples of R ₂ include a methylene group (-CH ₂ -), -CF ₂ -, an ethylene group (-C ₂ H ₄ -), -C ₂ H ₂ F ₂ -, a tetrafluoroethylene group (-C ₂ F ₄ -), and the like. Specific examples of R ₃ include,

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Representative examples of the monomer represented by the formula (1)

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등이 있다.

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On the other hand, the monomer represented by the formula (1) forms a lactone ring by an acid (H ⁺ ) as in the mechanism of the following reaction formula (1).

[Reaction Scheme 1]

In the case of the monomer (1), a lactone ring can be formed by self-bonding in the monomer. When the monomer containing X group is present together with the monomer as in the reaction scheme 1, the X group is released by the reaction with acid, For example, a carboxyl group (-COOH) or a hydroxy group (-OH) is formed, and bonding with other monomers in the polymer or bonding between polymers is possible. The monomer containing X group bonds with the mechanism of the reaction formula 1 by an acid formed by exposure to maintain hydrophobicity and forms a pattern by the difference in solubility with a region having hydrophilicity by an aqueous developer .

Next, the photosensitive polymer compound included in the coating composition for forming a fine pattern according to the present invention, which comprises the monomer of Formula 1, may be a conventional photosensitive polymer, and the use of the photosensitive polymer compound represented by Formula 2 Is most preferable.

(2)

로서, 상기 반응식 1에 나타낸 메커니즘과 같이, 산(H⁺)의 작용에 의해 형성된 히드록시기와, 에스터기 또는 산무수물의 반응에 의해 락톤 고리를 형성시키는 작용기이다. X는 상기 화학식 1의 R₃과 동일한 것으로서, 헤테로 원자 1 내지 20개를 포함하거나 포함하지 않는 탄소수 1 내지 25의 선형, 가지형 및/또는 고리형의 포화 또는 불포화 탄화수소기이며, 바람직하게는, 산소(O) 원자 및/또는 질소(N) 원자 등을 1 내지 10개 포함하거나 포함하지 않는 탄소수 4 내지 20의 선형, 가지형 및/또는 고리형의 포화 또는 불포화 탄화수소기이며, Y는 헤테로 원자 1 내지 20개를 포함하거나 포함하지 않는 탄소수 1 내지 25의 선형, 가지형 및/또는 고리형의 포화 또는 불포화 탄화수소기, 바람직하게는, 히드록시기(-OH) 또는 히드록시기 및 할로겐기로 치환된 산소(O) 원자 및/또는 질소(N) 원자 등을 1 내지 10개 포함하거나 포함하지 않는 탄소수 4 내지 20의 선형, 가지형 및/또는 고리형의 포화 또는 불포화 탄화수소기이다. a, b 및 c는 상기 화학식 2의 고분자를 구성하는 각각의 단량체 반복단위의 몰 퍼센트로서, 상기 a는 10 내지 100 몰%, 바람직하게는 10 내지 90 몰%, 더욱 바람직하게는 30 내지 80 몰%이고, 상기 b는 0 내지 50 몰%, 바람직하게는 5 내지 45 몰%, 더욱 바람직하게는 10 내지 30 몰%이며, 상기 c는 0 내지 50 몰%, 바람직하게는 5 내지 45 몰%, 더욱 바람직하게는 10 내지 30 몰%이다. 여기서, 상기 b 및 c 중 적어도 하나는 0 몰% 보다 커야 한다. 예를 들면, 상기 b 및 c 중 적어도 하나는 0.1 몰% 이상이어야 한다. 상기 각각의 단량체 반복단위의 몰 퍼센트가 상기 각각의 범위를 벗어날 경우, 포토레지스트막의 물성 저하 또는 형성의 어려움이 있을 수 있으며, 패턴의 콘트라스트(contrast)가 저하될 우려가 있다. 한편, 상기 반복단위 a, b 및 c 몰%의 합이 100 몰% 보다 적을 경우에는, 스티렌 등의 다른 단량체가 포함될 수도 있다.
In the general formula (2), R ₄ is a hydrogen atom or a methyl group, and R ₅ is a partial structure of the general formula

Is a functional group that forms a lactone ring by reaction of a hydroxyl group formed by the action of an acid (H ⁺ ) with an ester group or an acid anhydride, as in the mechanism shown in Scheme 1 above. X is the same as R ₃ in the above formula (1) and is a linear, branched and / or cyclic saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms, which may or may not contain 1 to 20 hetero atoms, Branched and / or cyclic saturated or unsaturated hydrocarbon group of 4 to 20 carbon atoms which contains 1 to 10 carbon atoms and / or nitrogen (N) atoms, and Y represents a hetero atom Branched or cyclic, saturated or unsaturated hydrocarbon group of 1 to 25 carbon atoms with or without 1 to 20 carbon atoms, preferably a hydroxyl group (-OH) or oxygen (O) substituted with a hydroxy group and a halogen group Branched and / or cyclic saturated or unsaturated hydrocarbon group of 4 to 20 carbon atoms, which may or may not contain 1 to 10 atoms and / or nitrogen (N) atoms. a, b and c are molar percentages of the respective monomer repeating units constituting the polymer of Formula 2, wherein a is 10 to 100 mol%, preferably 10 to 90 mol%, more preferably 30 to 80 mol% , B is 0 to 50 mol%, preferably 5 to 45 mol%, more preferably 10 to 30 mol%, c is 0 to 50 mol%, preferably 5 to 45 mol% And more preferably 10 to 30 mol%. Here, at least one of b and c should be larger than 0 mol%. For example, at least one of b and c should be at least 0.1 mol%. If the molar percent of each monomer repeating unit is out of the above range, the physical properties of the photoresist film may be lowered or difficult to form, and the contrast of the pattern may be lowered. On the other hand, when the sum of the repeating units a, b and c is less than 100 mol%, other monomers such as styrene may be included.

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등이 있다(한편, 상기 예에서 굴곡선(

)은, 상기 화학식 2의 X 및 Y가 산소(O) 원자와 결합되는 연결부(connecting bond)를 나타낸다).
Specific examples of X include the same as those exemplified for R ₃ in Formula 1, and specific examples of Y include, ,

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(In the above example, the curved line

) Represents a connecting bond in which X and Y in Formula 2 are bonded to an oxygen (O) atom.

The photosensitive polymeric compound represented by Formula 2 has a weight average molecular weight (Mw) of 2,000 to 20,000, preferably 3,000 to 12,000, and more preferably 5,000 to 10,000. The polydispersity index PDI ) Is from 1 to 2.5, preferably from 1.5 to 1.8. When the weight-average molecular weight and polydispersity are out of the above range, solubility in a solvent may be lowered or defects may occur in a photoresist film. The content of the photosensitive polymer compound is 3 to 30% by weight, preferably 4 to 10% by weight, based on the total coating composition for forming a fine pattern. If the content of the photosensitive polymer compound is less than 3% by weight, formation of a photoresist film and a pattern may become difficult. When the content of the photosensitive polymer compound exceeds 30% by weight, the thickness distribution of the pattern formed on the wafer may be uneven.

Next, a photo acid generator (PAG), which is used in the present invention and is represented by the following formula (3), can effectively control the acid diffusion length, thereby improving pattern resolution and line width roughness (LWR) Can be improved.

(3)

In Formula 3, R ₇ is a linear, branched and / or cyclic hydrocarbon group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, with or without an amine group (-NH 2). R ₈ , R ₉ and R ₁₀ are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, A linear or branched alkyl group such as a normal butyl group and a hexyl group, and an aromatic group such as a benzene group, a toluene group and a tertiary butylbenzene group. In Formula 3, Z is sulfur (S) or iodine (I), and when Z is iodine (I), R ₁₀ is not present. In addition, R ₄ , X, Y, a, b and c are the same as those described in Formula 2, and n is an integer of 0 to 6. g is 0 to 20 mol% of the repeating unit of the monomers constituting the polymer of formula (3) , Preferably 0.1 to 20 mol%, and more preferably 0.1 to 10 mol%. If it is out of the above range, the formation of the pattern is not easy, or the polymer may not be dissolved in the solvent due to the solubility problem of the polymer in the production of the photoresist composition, which causes defects in the pattern. On the other hand, when the sum of the repeating units a, b, c, and g mol% is less than 100 mol%, other monomers such as styrene may be included.

In the general formula (3), examples of the monomer moiety composed of R ₇ to R ₁₀ and Z include,

등이 있으며, 단일 또는 두 개 이상의 화합물을 혼합하여 사용할 수 있다.

Etc., and a single compound or two or more compounds may be used in combination.

The photoacid generator may be any compound capable of generating an acid in response to an actinic ray or radiation to serve as a chemically amplified resist composition in the photoresist composition according to the present invention. But the present invention is not limited to the photoacid generator of the present invention and may be a conventional sulfonium salt, iodonium salt, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type, Generators may also be used. The content of the photoacid generator is preferably 0.05 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the photosensitive polymer compound. When the amount of the photoacid generator is less than 0.05 part by weight, When the amount of the photoacid generator exceeds 30 parts by weight, the photoacid generator absorbs a large amount of ultraviolet rays and generates a large amount of acid, thereby obtaining an undesirable cross-sectional pattern. The weight average molecular weight (Mw) of the photoacid generator is 2,000 to 20,000, preferably 3,000 to 10,000.

Next, the acid diffusion controlling agent represented by the following formula (4) used in the present invention is capable of suppressing the diffusion rate when the acid (H ⁺ ) generated from the photo acid generator is diffused in the photoresist film The use of the acid diffusion control agent makes it easy to adjust the sensitivity of the photoresist, thereby improving the resolution of the pattern and reducing the width of the sensitivity variation, thereby improving the margin in exposure and the pattern profile.

[Chemical Formula 4]

In the general formula (4), R ₁₁ is a monovalent hydrocarbon group having 1 to 10 hetero atoms, preferably 1 to 20 carbon atoms, including 1 to 8 nitrogen (O), sulfur (S) And R < ₁₂ > and R < ₁₃ > are each hydrogen or contain 1 to 5 hetero atoms and preferably do not contain hetero atoms 2 to 4 Chain saturated and / or cyclic saturated or unsaturated hydrocarbon group containing 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. In addition, R ₄ , X and Y are the same as those described in Formula 2 above. H, i and j are molar percentages of the repeating unit of the monomer constituting the polymer of formula (4), h is 5 to 75 mol%, preferably 5 to 50 mol%, more preferably 10 to 45 mol% %, I and j are each independently 0 to 95 mol%, preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and at least one of i and j is larger than 0 mol% do. For example, at least one of i and j should be at least 0.1 mol%. On the other hand, when the sum of the recurring units h, i and j mol% is less than 100 mol%, other monomers such as styrene may be included.

The polymeric acid diffusion control agent represented by Formula 4 may be mixed with a basic acid diffusion control agent commonly used in a photoresist composition, and examples of the basic acid diffusion control agent may include, for example, The nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyl group, the N-oxides, the amides, the imides, the carbamates, and the ammonium salt of the first, second and third class aliphatic amines, aromatic amines, heterocyclic amines, And mixtures thereof may be used without limitation. The weight average molecular weight (Mw) of the acid diffusion controlling agent is 2,000 to 20,000, preferably 2,500 to 15,000, and the polydispersity index (PDI) is 1 to 2, preferably 1.2 to 1.8. If the weight average molecular weight and the polydispersity are out of the above range, the solubility in a solvent may be lowered or the contrast of a pattern may be lowered. The content of the acid diffusion controlling agent is 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the entire coating composition for fine pattern formation. If the amount is outside the above range, And the contrast of the pattern may be lowered.

The organic solvent used in the coating composition for forming a fine pattern according to the present invention can be used without limitation without modifying the photoresist pattern. Examples of the organic solvent include ethylene glycol monomethyl ethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monomethyl 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, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylformamide, N-methylpyrrolidone, - dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethyl propionate, 2-heptanone, Hydroxybutyl lactone, 2-hydroxypropion ethyl, 2-hydroxy-2-methylpropionic acid ethyl, ethoxy ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy- Methyl propionate, ethyl 3-ethoxypropionate, ethyl 3-methoxy-2-methylpropionate, ethyl acetate, butyl acetate and mixtures thereof may be used. For example, a single or a mixture of two or more and less than five Can be used.

The immersion polymeric compound represented by the following general formula (5), which contains the monomer of the general formula (1), may contain fluorine. The immersion lithography process may further include a photoresist By increasing the hydrophobicity of the film surface, it is possible to reduce the elution of the material of the photoresist film into the immersion solvent or to improve the water harvesting property.

[Chemical Formula 5]

In the general formula (5), R ₆ is a functional group containing an aliphatic hydrocarbon group having a polar group, and is a functional group containing 1 to 20 oxygen atoms and having 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms, And is a hydrocarbon group containing 3 to 15 linear, branched and / or cyclic fluoroalkyl groups and / or fluoro alcohol groups. Examples of the polar group include a hydroxy group (-OH), a cyano group (-CN), a carboxyl group (-COOH), and a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Is preferably a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom. The R ₆ may be used by mixing one or more species. In addition, R ₄ , X and Y are the same as those described in Formula 2 above. d, e and f are mole percentages of each monomer repeating unit constituting the polymer of formula (5), d is 5 to 75 mol%, preferably 5 to 50 mol%, more preferably 15 to 30 mol %, E is 0 to 95 mol%, preferably 5 to 90 mol%, more preferably 10 to 70 mol%, f is 0 to 50 mol%, preferably 5 to 30 mol% More preferably 15 to 25 mol%. Here, at least one of the e and f should be larger than 0 mol%. For example, at least one of e and f should be at least 0.1 mol%. If the molar percent of each monomer repeating unit deviates from the respective ranges, the desired contact angle may not be reached. On the other hand, when the sum of the repeating units d, e and f mol% is less than 100 mol%, other monomers such as styrene may be included.

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등이 있다(한편, 상기 예에서 굴곡선(

)은, 상기 화학식 3의 R₆이 산소(O) 원자와 결합되는 연결부(connecting bond)를 나타낸다).
Specific examples of R < ₆ >

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(In the above example, the curved line

Represents a connecting bond in which R _{6 in} Formula 3 is bonded to an oxygen (O) atom.

The liquid immersion polymer represented by Formula 5 has a weight average molecular weight (Mw) of 2,000 to 20,000, preferably 2,500 to 15,000, and more preferably 5,000 to 10,000. The polydispersity index PDI ) Is from 1 to 2, preferably from 1.2 to 1.8, and when the weight average molecular weight and polydispersity are out of the above range, the desired contact angle may not be reached. The content of the liquid immersion polymer compound is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the photosensitive polymer, and the content of the liquid immersion polymer compound is 100 parts by weight If the amount of the liquid immersion polymer compound is less than 0.5 parts by weight, the hydrophobic property of the surface of the photoresist film is lowered and the material of the photoresist film may elute into the immersion solvent or deteriorate water harvestability. Exceeds 10 parts by weight, the photoresist film may be defective.

The polymer additive represented by the following general formulas (6) to (8) is a resin containing silicon (Si) and can enhance the resistance to etching.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

의 구조를 가질 수 있다. 상기

구조에서, R₂₂는 탄소수 1 내지 9, 바람직하게는 탄소수 2 내지 8의 선형, 가지형 및/또는 고리형의 포화 탄화수소기이고, R₂₃은 각각 적어도 1개의 수소(H) 원자가 불소(F) 원자로 치환된 탄소수 1 내지 8, 바람직하게는 탄소수 2 내지 5의 탄화수소기이며, R₂₄는 수소(H) 원자이거나, 히드록시기(-OH) 또는 에스터기(-COO-)이거나, 탄소수 1 내지 30, 바람직하게는 탄소수 3 내지 27의 선형, 가지형, 단환형 및/또는 다환형의 알킬기를 포함하는 탄화수소기인 산해리성 수지이다. 또한, 화학식 6의 q는 1 내지 3의 정수이며, 화학식 8의 r은 4 내지 50의 정수이다(한편, 상기

구조에서 굴곡선(

)은 연결부(connecting bond)를 나타낸다).
(6) to (8) are polymers wherein R ₁₄ to R ₁₆ in Chemical Formula 6, R ₁₄ to R _{21 in} Chemical Formula 7 and R ₁₄ and R ₁₅ in Chemical Formula 8 are hydrogen (H) atoms or an alkyl group having 1 to 9 carbon atoms or

. ≪ / RTI > remind

R ₂₂ is a linear, branched and / or cyclic saturated hydrocarbon group having 1 to 9 carbon atoms, preferably 2 to 8 carbon atoms, and R ₂₃ is at least one hydrogen (H) Substituted hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 5 carbon atoms, R ₂₄ is a hydrogen (H) atom, a hydroxyl group (-OH) or an ester group (-COO-) Preferably an acid-dissociable resin which is a hydrocarbon group containing a linear, branched, monocyclic and / or polycyclic alkyl group having 3 to 27 carbon atoms. Q in the general formula (6) is an integer of 1 to 3, and r in the general formula (8) is an integer of 4 to 50

In the structure,

) Represents a connecting bond).

Examples of R ₁₄ to R ₂₁ in the general formulas (6) to (8)

,

,

,

,

,

등이 있다.

,

,

,

,

,

.

The method for forming a fine pattern of a semiconductor device using the coating composition for forming a fine pattern according to the present invention includes the steps of forming a photoresist film by applying the coating composition for forming a fine pattern on a semiconductor substrate having a pattern layer formed thereon, Exposing the photoresist film with an exposure mask and an exposing device, and developing the exposed photoresist film with an alkali water-soluble developer, which is a positive tone developing solution, to form a photoresist pattern.

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.

M-1 to M-17 are monomers for polymerizing the photosensitive polymer compound and the liquid immersion polymer compound contained in the coating composition for forming a fine pattern according to the present invention, M-12 and M-14 are monomers located in the X-position of the formula (2), M-15 and M-16 are monomers of the formula _The monomer positioned at the _6- position, M-17, is a lactone monomer.

[Preparation Example 1] Preparation of photosensitive polymer

M-1 and M-11 were mixed at a molar ratio of 50:50, and methyl ethyl ketone, an organic solvent, was added in the same amount as the amounts of the M-1 and M-11 to the amounts of the M-1 and M- 1.5 parts by weight, to obtain a monomer solution. Next, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), which are polymerization initiators, are added in an amount of 1 mol% to 5 mol, preferably 1 mol%, based on the amount of the M-1 and M- % Of methyl ethyl ketone to obtain a polymerization initiator solution. Next, a 500 ml three-necked flask charged with 50 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and the monomer solution and the polymerization initiator solution were heated at 80 占 폚 while stirring the flask for 3 hours / RTI > At the start of the polymerization, the polymerization reaction was carried out for 6 hours. After completion of the polymerization, the polymerization reaction solution was water-cooled, cooled to a temperature of 30 캜 or lower, put in a solvent mixed with 800 g of methanol and 200 g of water, and the precipitated white powder was filtered off. Next, the filtrated white powder was dispersed in 200 g of methanol to prepare a slurry, followed by washing and filtration. The filtration was carried out twice at a temperature of 50 캜 for 17 hours to obtain a white powder (Weight average molecular weight (Mw) = 9,000, polydispersity (PDI) = 1.75) at a yield of 67.5%.

[Production Examples 2 to 26] Preparation of Photosensitive Polymers

The polymer (photosensitive polymer) was obtained in the same manner as in Preparation Example 1, except that the M-1 to M-17 were mixed in the respective molar ratios shown in Tables 1 and 2, Molecular weight (Mw), polydispersity (PDI) and yield (%) are shown in Tables 1 and 2 below.

M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 Mw
PDI
yield(%)
M-9 M-10 M-11 M-12 M-13 M-15 M-17 Production Example 1
50 9,000
1.78
67.5
50 Production Example 2
60 8,500
1.68
66.3
40 Production Example 3
70 7,800
1.75
64.3
30 Production Example 4
80 7,900
1.78
60.3
20 Production Example 5
60 8,100
1.79
62.1
20 20 Production Example 6
60 8,200
1.69
62.3
20 20 Production Example 7
60 8,300
1.75
64.2
20 10 10 Production Example 8
50 7,800
1.73
63.4
40 10 Production Example 9
60 8,500
1.81
63.9
40 Production Example 10
60 8,900
1.82
62.8
40 Production Example 11
60 8,800
1.77
63.4
40 Production Example 12
60 8,500
1.88
64.5
40 Production Example 13
60 8,600
1.87
61.3
40

M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 Mw
PDI
yield(%)
M-9 M-10 M-11 M-12 M-13 M-15 M-17 Production Example 14
60 8,550
1.83
64
40 Production Example 15
60 8,700
1.84
66
40 Production Example 16
8,600
1.87
65.4
60 40 Production Example 17
8,400
1.79
65.7
60 40 Production Example 18
30 30 8,400
1.79
65
40 Production Example 19
30 30 8,100
1.71
63.3
40 Production example 20
30 30 8,300
1.76
61.5
40 Production Example 21
30 30 8,900
1.81
64.5
40 Production Example 22
30 30 8,800
1.79
63.5
40 Production Example 23
30 30 8,000
1.75
64.1
40 Production Example 24
30 8,600
1.87
65.5
30 40 Production example 25
30 7,800
1.73
64.6
30 40 Production Example 26
8,300
1.83
65.6
20 25 25 30

[Preparation Example 27] Preparation of immersion polymeric compound

The M-13 and the M-15 were mixed in a molar ratio of 70:30, and methyl ethyl ketone as an organic solvent was added to the same amount as that of the M-13 and M-15 to the amounts of the M-13 and M- 1.5 parts by weight, to obtain a monomer solution. Next, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile), which are polymerization initiators, are added in an amount of 1 mol% to 5 mol, preferably 1 mol%, based on the amount of the M-1 and M- % Of methyl ethyl ketone to obtain a polymerization initiator solution. Next, a 500 ml three-necked flask charged with 50 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and the monomer solution and the polymerization initiator solution were heated at 80 占 폚 while stirring the flask for 3 hours / RTI > At the start of the polymerization, the polymerization reaction was carried out for 6 hours. After completion of the polymerization, the polymerization reaction solution was water-cooled, cooled to a temperature of 30 캜 or lower, put in a solvent mixed with 800 g of methanol and 200 g of water, and the precipitated white powder was filtered off. Next, the filtrated white powder was dispersed in 200 g of methanol to prepare a slurry, followed by washing and filtration. The filtration was carried out twice at a temperature of 50 캜 for 17 hours to obtain a white powder (Weight average molecular weight (Mw) = 9,100, polydispersity (PDI) = 1.46) at a yield of 85.9%.

[Production Examples 28 to 30] Preparation of immersion polymeric compound

Polymers (liquid immersion polymers) were obtained in the same manner as in Preparation Example 27 except that the above-mentioned formulas M-13 to M-16 were mixed at the respective molar ratios set forth in Table 3 below. (Mw), polydispersity (PDI) and yield (%) are shown in Table 3 below.

M-13 M-14 M-15 M-16 Mw PDI yield(%) Production Example 27 70 30 9,100 1.46 85.9 Production Example 28 70 20 10 8,900 1.55 92.1 Production Example 29 70 30 9,000 1.49 89.5 Production Example 30 70 20 10 8,800 1.51 93.4

The coating compositions for fine pattern formation used in the following Examples were prepared by mixing the photosensitive polymer compounds and the liquid immersion polymer compounds prepared in Preparation Examples 1 to 30, the following photoacid generators 1 to 3, acid diffusion controllers 1 to 3, Organic solvent (1: propylene glycol monomethyl ether acetate, 2: gamma -butyrolactone, 3: methyl 2-hydroxyisobutylate, 4: propylene glycol monomethyl ether).

[Photo-generated acid 1]

[Photoelectric Generating Part 2]

(Mw=7,500)

(Mw = 7,500)

 [Pitch Generator 3]

[Acid diffusion control agent 1]

[Acid diffusion control agent 2]

(Mw=7,300)

(Mw = 7,300)

[Acid diffusion control agent 3]

[Polymer additives]

이고, R₁₅는 수소 원자로서, 상기 R₁₄ 및 R₁₅의 몰비는 6 : 4이며, 중량평균분자량(Mw)은 3,540이다)
(In the polymer additive, R < ₁₄ >

, R ₁₅ is a hydrogen atom, the molar ratio of R ₁₄ and R ₁₅ is 6: 4, and the weight average molecular weight (Mw) is 3,540)

[Examples 1 to 49, Comparative Example 1] Preparation of coating composition for fine pattern formation

The photosensitive polymer compound and the liquid immersion polymer compound prepared in Preparation Examples 1 to 30 and the photo acid generator, acid diffusion control agent and polymer additive were completely dissolved in a solvent according to the compositions shown in Tables 4 and 5, And filtered through a disk filter to prepare a coating composition for forming a fine pattern.

[Examples 1 to 49, Comparative Example 1] Fine pattern formation

An organic antireflection film composition DARC-A125 (manufacturer: Dongjin Semichem Co., Ltd.) was coated on a silicon (Si) wafer and then heated at 205 DEG C for 60 seconds to form an antireflection film of 35 nm. The coating composition prepared in Examples 1 to 49 and Comparative Example 1 was spin coated thereon and heated at 100 DEG C for 60 seconds to form a resist film having a thickness of 200 nm. Next, the wafer on which the resist film was formed was exposed using an ArF exposure apparatus (apparatus name: ASML 1200B, manufacturer: ASML Co.) having a numerical aperture of 0.85, heated at 100 ° C for 60 seconds, developed in 2.38% TMAH, The wafer was washed with DI water and rotated at 4000 rpm to obtain a hole pattern having a hole space of 90 nm and a hole line of 130 nm. On the other hand, in the case of Comparative Example 1, development was carried out using an organic solvent (butyl acetate).

[Examples 1 to 49, Comparative Example 1] Etching resistance of the coating composition for forming fine patterns

The photoresist compositions prepared in Examples 1 to 49 and Comparative Example 1 were coated on a wafer to a thickness of 3,000 ㅕ and heated at 110 캜 for 60 seconds (soft baking). Then, with the exception of a reticle (masking plate), the entire surface was exposed to light using an exposure mask and an ArF exposure apparatus (device name: ASML 1200B, manufactured by ASML Corporation) having a numerical aperture of 0.85 at 193 nm, Followed by post heating (post baking). Next, development was carried out with 2.38% TMAH, rinsed with DI water, and the wafer was rotated at 4000 rpm to remove the remaining cleaning liquid (rinsing liquid). Subsequently, dry etching (apparatus name: NE-5000N, manufacturer: ULVAC) was performed for 20 seconds at a CF ₄ / O ₂ / Ar gas flow rate of 50/20/150 sccm and RF power of 500 W, The results are shown in the following Tables 6 and 7 as relative ratios to the etching amounts when developing with an organic solvent (butyl acetate) of Comparative Example 1 in Table 7 (Comparative Example 1: 1.0). In the following Tables 6 and 7, EOP means the optimum exposure dose, and CD U means CD uniformity.

Performance evaluation EOP (mj) CDI (nm) The etching ratio of Comparative Example 1 Example 1 32 5.84 0.97 Great Example 2 32 5.81 0.97 Great Example 3 32 5.79 0.97 Great Example 4 32 5.88 0.97 Great Example 5 33 5.87 0.96 Great Example 6 33 5.77 0.96 Great Example 7 32 5.84 0.96 Great Example 8 32 5.83 0.96 Great Example 9 33 5.81 0.96 Great Example 10 36 5.81 0.96 Great Example 11 34 5.81 0.96 Great Example 12 34 5.82 0.96 Great Example 13 36 5.83 0.96 Great Example 14 32 5.83 0.96 Great Example 15 36 5.84 0.96 Great Example 16 34 5.83 0.96 Great Example 17 34 5.81 0.96 Great Example 18 33 5.81 0.97 Great Example 19 32 5.81 0.96 Great Example 20 33 5.82 0.95 Great Example 21 32 5.83 0.95 Great Example 22 32 5.77 0.93 Great Example 23 32 5.76 0.93 Great Example 24 32 5.78 0.93 Great Example 25 33 5.81 0.97 Great

Performance evaluation EOP (mj) CDI (nm) The etching ratio of Comparative Example 1 Example 26 33 5.81 0.97 Great Example 27 33 5.82 0.97 Great Example 28 33 5.83 0.97 Great Example 29 33 5.83 0.97 Great Example 30 33 5.84 0.97 Great Example 31 33 5.81 0.97 Great Example 32 33 5.81 0.97 Great Example 33 33 5.82 0.97 Great Example 34 33 5.83 0.97 Great Example 35 33 5.83 0.97 Great Example 36 35 5.84 0.97 Great Example 37 35 5.81 0.97 Great Example 38 35 5.82 0.97 Great Example 39 36 5.81 0.97 Great Example 40 33 5.81 0.97 Great Example 41 33 5.82 0.97 Great Example 42 33 5.83 0.97 Great Example 43 33 5.83 0.97 Great Example 44 33 5.84 0.97 Great Example 45 33 5.82 0.97 Great Example 46 33 5.83 0.97 Great Example 47 34 5.83 0.97 Great Example 48 34 5.84 0.97 Great Example 49 34 5.81 0.97 Great Comparative Example 1 40 6.84 1.0 -

As shown in Tables 6 and 7, in Examples 1 to 49, the CD uniformity value is smaller than that in Comparative Example 1, and a more uniform pattern is formed through the process using the alkali-soluble positive tone developer . In addition, it can be seen that Examples 1 to 49 all exhibited an etching relative ratio of 1 or less as compared with Comparative Example 1 using an organic solvent (butyl acetate). Therefore, when the coating composition for forming a fine pattern of the present invention is used, a positive tone alkaline water-soluble developer (TMAH and (2-hydroxyethyl) trimethyl ammonium hydroxide, etc.) It can be seen that the pattern formation is more advantageous due to the excellent etching rate.

Claims (11)

1. A coating composition for forming a fine pattern, comprising a photosensitive polymer comprising a monomer represented by the following formula (1), a photoacid generator, an acid diffusion controller, and an organic solvent.
[Chemical Formula 1]

Wherein R ₁ is a -CH ₂ CF ₃ group or a -CH ₂ OCH ₃ group, R ₂ is a linear or branched hydrocarbon group having 1 to 4 carbon atoms, which may or may not contain a fluorine (F) atom, or R ₃ is a linear or branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms, which may or may not contain 1 to 20 heteroatoms, R ₄ is a hydrogen atom or a methyl group, n is the number of repeating units of the hydrocarbon, The coating composition for fine pattern formation according to claim 1, wherein the photosensitive polymer compound is represented by the following formula (2).
(2)

In the general formula (2), R ₄ is a hydrogen atom or a methyl group, and R ₅ is a partial structure of the general formula

And X and Y are linear, branched and / or cyclic saturated or unsaturated hydrocarbon groups having 1 to 25 carbon atoms, with or without 1 to 20 heteroatoms, and a, b, and c are as defined in Formula Wherein a is from 10 to 100 mol%, and b and c are from 0 to 50 mol%, based on the molar percent of each monomer repeating unit constituting the polymer. The coating composition for fine pattern formation according to claim 1, wherein the photoacid generator is represented by the following formula (3).
(3)

In Formula 3, R ₄ are each a hydrogen atom or a methyl group, R ₇ is an amine group (-NH) include linear, branched of with or without 1 to 6 carbon atoms and / or a cyclic hydrocarbon group, R ₈ , R ₉ and R ₁₀ are each independently a hydrocarbon group having 1 to 10 carbon atoms, Z is sulfur (S) or iodine (I), and X and Y are each a group containing 1 to 20 hetero atoms A, b, c, and g are mole percentages of each monomer repeating unit constituting the polymer of Formula 3, and a is 10 To 100 mol%, b and c are 0 to 50 mol%, and g is 0 to 20 mol%. The photoacid generator according to claim 3, wherein the photoacid generator is a photoacid generator, a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide, an oxime-O- ≪ / RTI > and mixtures thereof. The coating composition for fine pattern formation according to claim 1, wherein the acid diffusion controlling agent is represented by the following formula (4).
[Chemical Formula 4]

Wherein R ₄ is a hydrogen atom or a methyl group, R ₁₁ is a chain and / or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms and 1 to 10 hetero atoms, R ₁₂ and R ₁₃ are each hydrogen or a chain and / or cyclic saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, with or without 1 to 5 heteroatoms, and X and Y include 1 to 20 heteroatoms And h, i and j are molar percentages of monomer repeating units constituting the polymer of formula (4), h is a molar ratio of 5 to 75 mol%, and each of i and j is independently 0 to 95 mol%. [5] The method of claim 5, wherein the acid diffusion controller is selected from the group consisting of first, second and third classes of aliphatic amines, aromatic amines, heterocyclic amines, nitrogen containing compounds having a carboxyl group, nitrogen containing compounds having a hydroxy group, Wherein the coating composition can be used in admixture with those selected from the group consisting of dewaxed, imidized, carbamates, ammonium salts, and mixtures thereof. [3] The method of claim 1, wherein the organic solvent is selected from the group consisting of 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 monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxypropyl N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethyl propionate, 2-heptanone, gamma-butyrolactone, -Butyrolactone, 2-hydroxypropionethyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, isopropyl, isobutyl, isobutyl, isobutyl, isobutyl, ≪ / RTI > The photosensitive resin composition according to claim 1, wherein the content of the photosensitive polymer compound is 3 to 30% by weight based on the coating composition for forming an entire fine pattern, the content of the photoacid generator is 0.05 to 30 parts by weight based on 100 parts by weight of the photosensitive polymer compound , The content of the acid diffusion controlling agent is 0.1 to 5% by weight based on the entire coating composition for fine pattern formation, and the balance is an organic solvent. The coating composition for fine pattern formation according to claim 1, wherein the weight average molecular weight of the photosensitive polymer compound, the photoacid generator, and the acid diffusion controlling agent is 2,000 to 20,000. The coating composition for fine pattern formation according to claim 1, wherein the coating composition for fine pattern formation further comprises an immersion polymer compound represented by the following formula (5).
[Chemical Formula 5]

In Formula 5, R ₄ is a hydrogen atom or a methyl group, R ₆ is a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms containing 1 to 20 fluorine atoms, And / or a hydrocarbon group containing a cyclic, fluoroalkyl group and / or fluoro alcohol group, and X and Y are linear, branched and / or cyclic alkyl groups having 1 to 25 carbon atoms, which may or may not contain 1 to 20 hetero atoms And d is from 5 to 75 mol%, e is from 0 to 95 mol%, and d is from 5 to 75 mol% And f is 0 to 50 mol%. Forming a photoresist film by applying the coating composition for fine pattern formation according to claim 1 on a semiconductor substrate having a patterned layer formed thereon;
Exposing the photoresist film with an exposure mask and an exposure apparatus; And
Forming a photoresist pattern by developing with an alkali water-soluble developer which is a positive tone developer.