KR101855507B1 - Composition for coating photoresist pattern developed by negative tone developer and method of forming fine pattern using the same - Google Patents

Abstract

상기 화학식 1에서, R₁은 수소 원자 또는 메틸기이고, R₂ 및 R₃은 각각 독립적으로 산소 원자 또는 질소 원자를 1 내지 4개 포함하거나 포함하지 않는 탄소수 1 내지 7의 선형 또는 분지형 탄화수소기이고, R₂ 및 R₃은 서로 연결되어 고리를 형성할 수 있으며, X는 존재하지 않거나, 산소 원자를 1 내지 3개 포함하거나 포함하지 않는 탄소수 1 내지 3의 선형 또는 분지형 탄화수소기이다.Disclosed is a composition for a photoresist pattern coating and a method for forming a fine pattern using the same, which is developed with a negative tone developer capable of forming a coating film on the surface of a photoresist pattern developed with a negative tone developing solution and reducing the size or diameter of a line width of the pattern. The composition for photoresist pattern coating developed with the negative tone developer includes a liposoluble polymer compound having a polarity (log P) of 1.0 to 8.0 and comprising a repeating unit represented by the following formula (1); And an organic solvent having 4 to 12 carbon atoms and containing 1 to 4 oxygen atoms.
[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently a linear or branched hydrocarbon group having 1 to 7 carbon atoms which may or may not contain an oxygen atom or a nitrogen atom , R ₂ and R ₃ may be connected to each other to form a ring, and X is not a linear or branched hydrocarbon group having 1 to 3 carbon atoms which does not contain or contains 1 to 3 oxygen atoms.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for coating a photoresist pattern, which is developed with a negative tone developer, and a method for forming a fine pattern using the composition.

The present invention relates to a composition for coating a photoresist pattern developed with a negative tone developer and a method for forming a fine pattern using the same, and more particularly, to a method for forming a coating film on a surface of a photoresist pattern formed by a pattern forming method using a negative tone developer To a negative tone developer capable of reducing the line width size or diameter of the pattern, and a method for forming a fine pattern using the same.

As the miniaturization and integration of semiconductor devices, it is required to realize a fine pattern. As a method for forming such a fine pattern, development of an exposure apparatus or miniaturization of a photoresist pattern through introduction of an additional process (for example, Reduction of pattern space through pattern coating process) is most effective.

As a photoresist pattern forming method, there are a pattern forming method using a negative tone developing liquid and a pattern forming method using a positive tone developing liquid. The pattern forming method using the positive tone developer is to selectively dissolve and remove the exposed area of the photoresist film with a positive tone developer to form a pattern. In the pattern formation method using the negative tone developer, a non-exposed area is selectively To form a pattern. The method of forming a pattern using the negative tone developer can be applied to a contact hole pattern or a trench pattern which is difficult to form due to insufficient exposure amount when a pattern forming method using a positive tone developer is used. A pattern can be easily formed, and a photoresist pattern (fine pattern) can be formed more effectively because an organic solvent is used as a developer for removing unexposed portions.

In addition, as a method for refining the photoresist pattern (fine pattern) through the introduction of the additional process, there is a pattern coating process for making the space portion of the formed photoresist pattern smaller. The pattern coating process is a method of forming a (fine) fine pattern by coating a coating composition containing a commonly used water-soluble polymer on a pattern and forming a coating layer having a uniform thickness on the pattern.

However, when applying (coating) a coating composition (conventional coating composition) containing the water-soluble polymer to a pattern (photoresist pattern developed with a negative tone developer) formed by a pattern formation method using a negative tone developer, The photoresist pattern developed with a developing solution is a pattern formed by a pattern forming method using a conventional positive tone developer (a ratio of the pattern (photosensitive polymer) deprotecting group to a carboxyl group (-COOH) ), The crosslinking reaction rate with the water-soluble polymer having a high nitrogen content and a high polarity of the polymer resin is increased, and the excess pattern is made finer.

Therefore, in the case of a coating compound using a conventional water-soluble polymer, it is difficult to miniaturize a fine pattern (for example, a line and space pattern of 50 nm or less or a contact hole pattern of 60 nm or less) due to excessive refinement, It is difficult to obtain a stable line width because of the large amount of change (the amount of change in the thickness of the coating film), and there is a problem in that the rate of occurrence of foreign matter (scum) increases in the pattern, the lower film quality (the interface between the pattern space and the pattern) Also, when the pH of the composition for pattern coating using a conventional water-soluble compound is 9 or more, the phenomenon that the photoresist pattern developed with the negative tone developer by the basic substance in the coating process of the coating composition and the pattern of the developed photoresist pattern are melted There is a possibility of occurrence.

Accordingly, it is an object of the present invention to provide a method for forming a pattern using a coating film, a method of forming a pattern using the coating composition, A method for forming a fine pattern using the same, and a method for forming a fine pattern using the same.

In order to achieve the above object, the present invention relates to a lipophilic polymer compound having a polar (log P) of 1.0 to 8.0 and comprising a repeating unit represented by the following formula (1); And a negative tone developer comprising an organic solvent having 4 to 12 carbon atoms and containing 1 to 4 oxygen atoms.

[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently a linear or branched hydrocarbon group having 1 to 7 carbon atoms which may or may not contain an oxygen atom or a nitrogen atom , R ₂ and R ₃ may be connected to each other to form a ring, and X is not a linear or branched hydrocarbon group having 1 to 3 carbon atoms which does not contain or contains 1 to 3 oxygen atoms.

The present invention also provides a method of manufacturing a semiconductor device, comprising: forming a photoresist film on a semiconductor substrate on which an etching layer is formed; Exposing the photoresist film to exposure and development with a negative tone developer to form a developed photoresist pattern with a negative tone developer; Applying a photoresist pattern coating composition developed with the negative tone developer onto the photoresist pattern developed with the negative tone developer; And a step of forming a coating film by heating and developing the photoresist pattern developed with the negative tone developing solution coated with the composition for photoresist pattern coating developed with the negative tone developing solution at 80 to 180 ° C to form a coating film, Lt; / RTI >

The composition for photoresist pattern coating developed with the negative tone developing solution according to the present invention comprises a liposoluble polymer compound containing nitrogen and an organic solvent and is characterized in that the photoresist pattern developed with a negative tone developing solution is coated with a water- It is possible to prevent defects (such as a phenomenon of melting of the pattern, a change in the pattern line width depending on the temperature, generation of foreign matter, etc.) when the composition is used. In addition, since the coating composition of the present invention can maximize the difference in dissolution rate between the portion where the coating film is formed and the remaining portion which is removed in the developing process, compared with a conventional coating composition using a water-soluble polymer, It is effective to implement the pattern and since the amount of change (? CD (nm)) of the pattern line width according to the temperature is small, a more stable pattern line width can be realized in semiconductor production. Further, since the coating composition of the present invention uses an organic solvent (which can use the same developer as the negative tone developer) at the time of development after the formation of the coating film, the development equipment used in the pattern formation process is used without the need of installing an additional developing unit It is economical.

Hereinafter, the present invention will be described in detail.

The composition for photoresist pattern coating developed with the negative tone developer according to the present invention may be formed by forming a coating film on a photoresist pattern (a photoresist pattern developed with a negative tone developer) formed by a pattern forming method using a negative tone developer, Soluble polymer containing a repeating unit represented by the following formula (1) and having a polarity (log P) of from 1.0 to 8.0, and a repeating unit represented by the following formula (1) Of an organic solvent.

Wherein R ₁ is a hydrogen atom (H) or a methyl group, R ₂ and R ₃ are each independently a straight or branched alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms, which does not contain an oxygen atom (O) or a nitrogen atom To 7, preferably 1 to 4, linear or branched hydrocarbon groups, and R ₂ and R ₃ may be connected to each other to form a ring. X does not contain a linear or branched hydrocarbon group having 1 to 3 carbon atoms, for example, a carbonyl group (-CO-) or an ester group (-COO-), which may or may not contain 1 to 3 oxygen atoms Is an alkyl group having 1 to 3 carbon atoms.

The oil-soluble polymer compound to be used in the present invention has a polar (log P) of 1.0 to 8.0, preferably 1.1 to 7.0, more preferably 1.2 to 6.0, and contains at least one nitrogen atom (amine group) As a result, when heated at a high temperature (80 to 180 ° C), a coating film can be formed on the pattern surface by crosslinking reaction with the photosensitive polymer on the surface of the photoresist pattern developed with the negative tone developer.

The log P is a value indicating a polarity such as a polymer or a single molecule. When the log P value is less than 1.0, the solubility in water is low, the solubility in an organic solvent is low, and the log P value is low If it is 1.0 or more, the solubility in water is lowered but the solubility in the organic solvent having a similar polarity value (log P = 1.2 to 3.0) is improved. The value of the polarity (log P) can be obtained in various ways, and the polarity (log P) value of the present invention is obtained through Crippen's fragmentation method. The method is described in detail in J. Chem. Inf. Com. Sci., 27, 21 (1987). When the polarity (log P) of the oil-soluble polymer compound is less than 1.0 or more than 8.0, there is a possibility that the oil-soluble polymer compound may not be dissolved in the organic solvent due to the polarity difference with the organic solvent used in the present invention.

Representative examples of the oil-soluble polymer compound containing the repeating unit represented by the formula (1) include homopolymers composed of only the repeating units represented by the formula (1), oil-soluble polymer compounds represented by the following formula (2) have.

In Formula 2, R < _{1 >} To R < ₃ > and X are as defined in the above formula (1), R < ₄ > is a hydrogen atom or a methyl group, and R < ₅ > is an alkyl group having 1 to 13, preferably 1 to 10 Linear or branched hydrocarbon group having 1 to 3 carbon atoms, Y is not present, or a linear or branched hydrocarbon group having 1 to 3 carbon atoms, which may or may not contain 1 to 3 oxygen atoms, for example, a carbonyl group (-CO-) , And an ester group (-COO-), and a and b are mole% of the repeating units constituting the polymer, and a is, for example, 1 to 99 mol% Is 2 to 80 mol%, more preferably 5 to 50 mol%, and b is, for example, 1 to 99 mol%, preferably 20 to 98 mol%, and preferably 50 to 95 mol%. Here, when a is less than 1 mol% (b is more than 99 mol%), there is a concern that the nitrogen radicals are insufficient in the oil-soluble polymer and a crosslinking reaction does not occur on the pattern surface (a fine pattern may not be formed).

Representative examples of the homopolymer having only the repeating unit or repeating unit represented by the formula (1) include homopolymers composed only of the repeating units or repeating units represented by the following formulas (1a) to (1c) Representative examples of the polymer compound include the oil-soluble polymer compounds represented by the following general formulas (2a) to (2q).

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(2i)

(2j)

[Chemical Formula 2k]

≪ EMI ID =

[Formula 2m]

(2n)

(2o)

[Chemical Formula 2p]

[Formula 2q]

In Formulas (2a) to (2q), a and b are the same as defined in Formula (2).

The content of the oil-soluble polymer compound is 0.5 to 15% by weight, preferably 1 to 10% by weight, and more preferably 3 to 8% by weight based on the composition for photoresist pattern coating developed with the entire negative tone developer. If the content of the oil-soluble polymer compound is less than 0.5% by weight, the coating film may be difficult to form. If the content is more than 15% by weight, the uniformity of the coating film may be poor. The weight-average molecular weight of the oil-soluble polymer compound is 2,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 15,000. If the weight-average molecular weight of the oil-soluble polymer compound is less than 2,000, there is a fear that coating performance (coating film formation becomes difficult) during coating, and if it exceeds 100,000, solubility in an organic solvent may drop sharply. The pH of the oil-soluble polymer may be 7.0 to 8.5.

The organic solvent used in the present invention does not modify the photoresist pattern developed with the negative tone developer when coating and forming a coating film, and is an organic solvent having 4 to 12 carbon atoms and containing 1 to 4 oxygen atoms, for example, A solvent having an acetate structure, an ether structure, an alcohol structure, or a ketone structure can be used, and preferably n-butyl acetate, diisobutyl ether, n-hexanol, n-heptanol, methyl isobutyl ketone, Etc. may be used. The content of the organic solvent is the same as that of the composition for coating a photoresist pattern developed with the entire negative tone developer except for the oil-soluble polymer.

The composition for photoresist pattern coating developed with the negative tone developer according to the present invention may further contain additives such as an acid catalyst, a surfactant, and a basic compound, if necessary.

The acid catalyst used in the present invention is one capable of improving the degree of crosslinking or crosslinking of a film when forming a coating film and includes, for example, hydrochloric acid, sulfuric acid, phosphoric acid, methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, P-toluenesulfonic acid (PTSA), camphorsulfonic acid, naphthylsulfonic acid, cyclohexylsulfonic acid, acetic acid, ethyl acetic acid, propyl acetic acid, isopropyl acetic acid, and mixtures thereof have. When the acid catalyst is used, the content of the acid catalyst is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer. If the content of the acid catalyst is less than 0.1 parts by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer, there is a possibility that the effect of improving the crosslinking degree or crosslinking ratio of the film may not be obtained. , There is a fear that the amount of crosslinking increases sharply due to excessive catalytic action due to excessive acid.

The surfactant used in the present invention is to increase the coatability of the coating composition. Conventional surfactants can be used. For example, depending on the size and thickness of the pattern, an anionic surfactant, a cationic surfactant, The amphoteric surfactants may be used alone or in combination of two or more. More specific examples of the surfactant include an alkylbenzenesulfonate surfactant, a higher amine halide, a quarternary ammonium salt surfactant, an alkyl pyridinium salt surfactant, an amino acid surfactant, and a sulfonimide surfactant . When the surfactant is used, the content of the surfactant is 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer. If the content of the surfactant is less than 0.01 part by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer, there is a fear that the uniformity of the coating film is lowered when the coating film is formed, , The coating film quality may be deteriorated due to the foam generated by the surfactant during the formation of the coating film, or the photoresist pattern may be lost due to excessive surfactant during the process of developing the coating film.

The basic compound used in the present invention acts as a cross-linking agent and a stabilizing agent, and typical amine compounds can be used. Examples thereof include triethanolamine (TEOA), 2-aminoethanol, 2- 2- (2-aminoethoxy) ethanol, and the like can be used. When the basic compound is used, the content of the basic compound is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer 0.1 to 0.5 parts by weight. If the amount of the basic compound is less than 0.01 parts by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the negative tone developer, there is a fear that the effect of using the basic compound may not be obtained. If the amount is more than 2 parts by weight, There is a fear that the basicity of the coating composition increases, and the surface of the photoresist pattern may be denatured upon coating.

The method for forming a fine pattern of a semiconductor device using the composition for photoresist pattern coating according to the present invention includes the steps of: (a) forming a photoresist film on a semiconductor substrate having a pattern layer formed thereon; (b) Forming a photoresist pattern developed with a negative tone developing solution by using a conventional negative tone developer such as n-butyl acetate to form a developed photoresist pattern; (c) Applying a photoresist pattern coating composition developed with the negative tone developer onto the photoresist pattern, (d) applying a photoresist pattern coating composition developed with the negative tone developer to the negative tone developer coated with the negative tone developer, The pattern was heated to 80 to 180 DEG C, and a tube of n-butyl acetate or the like By developing of a negative tone developer, it may include the step of forming a coating film.

The method for forming a fine pattern of a semiconductor device is a method of forming a conventional coating film using a coating composition according to the present invention on a photoresist pattern developed with a negative tone developer formed by a photoresist pattern forming method using a conventional negative tone developer Unlike the case of using a conventional coating liquid composition (a coating liquid composition containing a water-soluble polymer), it is not necessary to provide an additional developing unit, and the utilization rate of the equipment can be increased.

In the step (d), the photosensitive polymer on the surface of the developed photoresist pattern is crosslinked to form a coating film with the applied coating composition and a negative tone developing solution. The heating temperature in the heating process is 80 To 180 캜, preferably 130 to 150 캜, and the heating time is 5 to 300 seconds, preferably 50 to 90 seconds. If the heating temperature in the heating process is less than 80 ° C or the heating time is less than 5 seconds, a coating film (protective film) may not be formed on the photoresist pattern. If the heating temperature exceeds 180 ° C or the heating time is 300 seconds , There is a fear that the photoresist pattern is melted.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.

[Preparation Example 1] Preparation of the oil-soluble polymer represented by the formula (1a)

69.5 g (0.5 mol) of 1-vinyl-2-azepanone and 7.0 g of azobis (isobutyronitrile) (AIBN) were placed in a nitrogen-refluxed 500 mL reactor, After dissolving in 200 g of ethyl ketone (MEK), polymerization was carried out at 80 DEG C for 24 hours. After completion of the polymerization reaction, the reaction product was slowly added dropwise to diethyl ether and precipitated. After drying using a dry oven, the reaction product was again dissolved in methyl ethyl ketone, and the dissolved reaction product was reprecipitated in diethyl ether 59.2 g (yield: 85%) of the oil-soluble polymer represented by the above formula (1a) (homopolymer consisting only of the repeating unit represented by the formula (1a)) was obtained. The weight average molecular weight (Mw) and polydispersity (PD) of the polymer synthesized by GPC (Gel Permeation Chromatography) were analyzed and the polarity (log P) value was obtained by Crippen's fragmentation method (Mw = 11,120, PD = 1.85, and polarity (log P) = 1.64).

[Preparation Example 2] Preparation of the oil-soluble polymer represented by the formula (2a)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Except that 12.9 g (0.15 mol) of acrylic acid methyl ether and 12.9 g (0.15 mol) of acrylic acid methyl ether were used in place of acrylic acid methyl ether (a = 70 mol%, b = 30% by mole) (yield: 72%, Mw = 9,500, PD = 1.75, polarity (log P) = 2.60).

[Preparation Example 3] Preparation of the oil-soluble polymer represented by the formula (2b)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Except that 19.2 g (0.15 mol) of acrylic acid tetra buthyl ether was used instead of acrylic acid tetrabutyl ether (a = 70 mol%), b = 30 mol%) (yield: 84%, Mw = 9,160, PD = 1.81, polarity (log P) = 3.48).

[Preparation Example 4] Preparation of the oil-soluble polymer represented by the formula (2c)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Except that 23.1 g (0.15 mol) of acrylic acid cyclohexyl ether and 23.1 g (0.15 mol) of acrylic acid cyclohexyl ether were used in place of the acrylic acid cyclohexyl ether (a = 70 mol%, b = 30 mol%) (yield: 85%, Mw = 8,760, PD = 1.80, polarity (log P) = 4.15).

[Preparation Example 5] Preparation of the oil-soluble polymer represented by the formula (2d)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Except that 24.9 g (0.15 mol) of acrylic acid bicyclo [2.2.1] heptan-2-yl ether was used instead of acrylic acid bicyclo [2.2.1] heptan- (Yield: 71%, Mw = 9,620, PD = 1.72, polarity (log P) = 3.96) was obtained in the same manner as the oil soluble polymer represented by Formula 2d (a = 70 mol%, b = 30 mol% ).

[Preparation Example 6] Preparation of the oil-soluble polymer represented by the formula (2e)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, And 30.9 g (0.15 mol) of acrylic acid octahydro-4,7-methano-inden-5-yl ether were used in place of the acrylic acid octahydro- (Yield: 78%, Mw = 8,600, PD = 1.64, polarity: (a = 70 mol%, b = 30 mol%) represented by the formula 2e was obtained in the same manner as in Preparation Example 1 log P) = 3.84).

[Preparation Example 7] Preparation of the oil-soluble polymer represented by the formula (2f)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Soluble polymer represented by the above formula (2f) was obtained in the same manner as in Preparation Example 1, except that 30.9 g (0.15 mol) of acrylic acid adamatan-1-yl ether was used instead of acrylic acid adamantan- (Yield: 69%, Mw = 9,450, PD = 1.65, polarity (log P) = 3.73) was obtained as a compound (a = 70 mol%, b = 30 mol%).

[Preparation Example 8] Preparation of a liposoluble polymer represented by the formula (2g)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, Except that 17.4 g (0.15 mol) of acrylic acid 2-hydroxy-ethyl ether was used in place of the acrylic acid 2-hydroxy-ethyl ether (yield: 84%, Mw = 9,860, PD = 1.86, polarity (log P) = 2.02).

[Preparation Example 9] Preparation of a liposoluble polymer represented by the formula (2h)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, acrylic Acid and 5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7] non-2-yl ether (acrylic acid 5-oxo-4 -oxa- tricyclo [4.2.1.0 3,7] non-2 64.0 g of the oil soluble polymer (a = 70 mol%, b = 30 mol%) represented by the formula 2h was obtained in the same manner as in Preparation Example 1, except that 33.3 g (0.15 mol) (Yield: 78%, Mw = 9,210, PD = 1.94, polarity (log P) = 2.78).

[Preparation Example 10] Preparation of the oil-soluble polymer represented by the formula (2i)

(0.35 mol) of 1-vinyl-2-azepanone was used instead of 69.5 g (0.5 mol) of the 1-vinyl-2-azepanone, acrylic Acid and 5-oxo-4,8-dioxa-tricyclo [4.2.1.0 ^3,7] non-2-yl ether (acrylic acid 5-oxo-4,8 -dioxa-tricyclo [4.2.1.0 3, ^{7] non-2-yl ether} ) 33.6g (0.15mol) , and is oil-soluble polymer compound in the same manner as in Preparation example 1 of the formula 2i except for using (a = 70% mol, b = 30 moles (Yield: 90%, Mw = 8,990, PD = 1.90, polarity (log P) = 1.76).

[Preparation Example 11] Preparation of a fat-soluble polymer represented by the formula (2j)

Vinyl-pyrrolidone (38.9 g, 0.35 mol) and 2-vinyl-2-azepanone were used in the place of 69.5 g (0.5 mol) of 1-vinyl- Except that 15.0 g (0.15 mol) of 2-methyl acrylic acid methyl ether was used in place of methyl acrylate methyl ether (a = 70 mol%) in the same manner as in Preparation Example 1, (yield: 95%, Mw = 8,120, PD = 1.80, polarity (log P) = 1.77).

[Preparation Example 12] Preparation of the oil-soluble polymer represented by the formula (2k)

(0.35 mol) of 1-vinyl-imidazole instead of 69.5 g (0.5 mol) of 1-vinyl-2-azepanone and 2-methyl Except that 15.0 g (0.15 mol) of 2-methyl acrylic acid methyl ether was used in place of 70% by mole of the oil-soluble polymer represented by Formula 2k (a = 70 mol% (yield: 98%, Mw = 9,480, PD = 1.68, polarity (log P) = 1.68).

[Preparation Example 13] Preparation of the oil-soluble polymer represented by the formula (1b)

Azepan-1-yl-propenone 76.6 (0.5 mol) was used instead of the above-mentioned 1-vinyl-2-azepanone 52.1 g of a liposoluble polymer compound (a homopolymer consisting only of a repeating unit represented by the formula (1b)) represented by the above formula (1b) was obtained in the same manner as in the above Production Example 1 except for using 0.5 g (0.5 mol) %, Mw = 13,050, PD = 1.77, and polarity (log P) = 2.30).

[Preparation Example 14] Preparation of the oil-soluble polymer represented by the formula (1c)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) except that 69.6 g (0.5 mol) of 2-pyrrolidin-1-yl-propenone was used instead of 69.6 g (0.5 mol) of the repeating unit represented by formula ) (Yield: 78%, Mw = 11,560, PD = 1.58, polarity (log P) = 1.76).

[Preparation Example 15] Preparation of a fat-soluble polymer represented by the formula (21)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) (0.15 mol) of 2-methyl acrylic acid methyl ether was used instead of 48.7 g (0.35 mol) of 3-pyrrolidin-1-yl-propenone (Yield: 82%, Mw = 12,080, PD = 1.95, polarity (log P) = 3.14) was obtained in the same manner as in Example 1, .

[Preparation Example 16] Preparation of a fat-soluble polymer represented by the formula (2m)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) (0.15 mol) of 2-methyl acrylic acid tetra buthyl ether was used instead of 48.7 g (0.35 mol) of 2-methylpyrrolidin-1-yl- (Yield: 85%, Mw = 12,810, PD = 1.82, polarity (log P) = 60) was obtained in the same manner as in Synthesis Example 1, 4.02).

[Preparation Example 17] Preparation of a fat-soluble polymer represented by the formula (2n)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) except that 27.0 g (0.15 mol) of 2-methyl acrylic acid cyclohexyl ether (48.7 g, 0.35 mol) was used instead of 2-methyl-acrylic acid cyclohexyl ether (Yield: 86%, Mw = 10,010, PD = 1.84, polarity (log P) = 30) was obtained in the same manner as in the preparation of the oil-soluble polymer (a = 70 mol% 4.69).

[Production Example 18] Preparation of a fat-soluble polymer represented by the formula ( 2)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) 2-methyl acrylic acid bicyclo [2.2.1] heptan-2-yl (0.35 mol) and 2-methyl acrylic acid bicyclo [2.2.1] heptan- (a = 70 mol%, b = 30 mol%) represented by the formula 2 o was obtained in the same manner as in Preparation Example 1, except that 27.0 g (0.15 mol) of Yield: 76%, Mw = 13,220, PD = 1.73, polarity (log P) = 4.50).

[Preparation Example 19] Preparation of the oil-soluble polymer represented by the formula (2p)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) 2-methyl acrylic acid octahydro-4,7-methano-inden-5-yl ether (48.7 g, 0.35 mol) (a = 70 mol%, b = 30 mol%) represented by Formula 2p was obtained in the same manner as in Preparation Example 1, except that 33.0 g (0.15 mol) of inden- (Yield: 69%, Mw = 11,960, PD = 1.67, polarity (log P) = 5.08).

[Preparation Example 20] Preparation of the oil-soluble polymer represented by the formula (2q)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) pyrrolidin-1-yl-propenone) and 33.0 g (0.15 mol) of 2-methyl acrylic acid adamatan-1-yl ether were used (Yield: 75%, Mw = 11,560, PD = 30) was obtained in the same manner as in Production Example 1, except that the amount of the oil-soluble polymer represented by the formula 2q was 70 mol% 1.82, polarity (log P) = 4.97).

[Preparation Example 21] Preparation of the oil-soluble polymer represented by the formula (2q)

Methyl-1-pyrrolidin-1-yl-propenone was used instead of the above-mentioned 1-vinyl-2-azepanone (69.5 g, 0.5 mol) 55.1 g (0.25 mol) of 2-methyl acrylic acid adamatan-1-yl ether was used in place of 34.8 g (0.25 mol) of 2-methylpyrrolidin- (Yield: 59%, Mw = 9,810, PD: 50%) was obtained in the same manner as in Preparation Example 1, 1.59, and polarity (log P) = 5.80).

[Examples 1-1 to 1-24 and Comparative Example 1] The development with a negative tone developer Preparation of composition for photoresist pattern coating

(a=70, b=30, 분자량=9,500, 극성(log P)=-0.59)), 지용성 및 수용성 계면활성제인 3M사의 FC4430, 염기성 화합물(트리에탄올 아민(TEOA)) 및 산촉매 화합물(파라톨루엔 술폰산(PTSA))을 용매(n-부틸 아세테이트(nBA), n-헵탄올, 탈이온수)에 완전히 용해시킨 후, 0.2㎛의 디스크 필터로 여과하여 네가티브 톤 현상액으로 현상된 포토레지스트 패턴 코팅용 조성물을 제조하였다.According to the composition shown in the following Table 1, the oil-soluble polymer compound (Preparation Examples 1 to 1-21) or the water-soluble polymeric compound A1 (

(a = 70, b = 30, molecular weight = 9,500, polarity (log P) = -0.59)), fat soluble and water soluble surfactant FC4430, basic compound (triethanolamine (TEOA)) and acid catalytic compound (paratoluenesulfonic acid (PTSA)) was completely dissolved in a solvent (n-butyl acetate (nBA), n-heptanol, deionized water) and then filtered with a 0.2 mu m disk filter to prepare a composition for photoresist pattern coating .

Polymer compound Surfactants additive
(usage) Organic solvent Manufacturing example usage compound usage nba n-heptanol Example 1-1 One 8.0 g FC 4430 0.1 g - 91g - Examples 1-2 2 8.0 g FC 4430 0.1 g - 91g - Example 1-3 3 8.0 g FC 4430 0.1 g - 91g - Examples 1-4 4 8.0 g FC 4430 0.1 g - 91g - Examples 1-5 5 8.0 g FC 4430 0.1 g - 91g - Examples 1-6 6 8.0 g FC 4430 0.1 g - 91g - Examples 1-7 7 8.0 g FC 4430 0.1 g - 91g - Examples 1-8 8 8.0 g FC 4430 0.1 g - 91g - Examples 1-9 9 8.0 g FC 4430 0.1 g - 91g - Example 1-10 10 8.0 g FC 4430 0.1 g - 91g - Example 1-11 11 8.0 g FC 4430 0.1 g - 91g - Examples 1-12 12 8.0 g FC 4430 0.1 g - 91g - Examples 1-13 13 8.0 g FC 4430 0.1 g - 91g - Examples 1-14 14 8.0 g FC 4430 0.1 g - 91g - Examples 1-15 15 8.0 g FC 4430 0.1 g - 91g - Examples 1-16 16 8.0 g FC 4430 0.1 g - 91g - Examples 1-17 17 8.0 g FC 4430 0.1 g - 91g - Example 1-18 18 8.0 g FC 4430 0.1 g - 91g - Example 1-19 19 8.0 g FC 4430 0.1 g - 91g - Examples 1-20 20 8.0 g FC 4430 0.1 g - 91g - Examples 1-21 21 8.0 g FC 4430 0.1 g - 91g - Examples 1-22 7 8.0 g FC 4430 0.1 g TEOA (0.2 g) 91g - Examples 1-23 7 8.0 g FC 4430 0.1 g PTSA (0.2 g) 91g - Examples 1-24 7 8.0 g FC 4430 0.1 g - 70g 21g Comparative Example 1 A1 8.0 g FC 4430 0.1 g - Deionized water 91 g

[Examples 2-1 to 2-24 and Comparative Example 2] Formation and evaluation of fine patterns of semiconductor devices

ArF organic antireflective film composition DARC-A125 (manufacturer: Dongjin Semichem Co., Ltd.) was coated on a silicon wafer to a thickness of 33 nm and heated at 240 캜 for 60 seconds and then photoresist composition DHA-7079 (ArF photoresist, Dongjin Semichem Co.) was coated and heated at 105 캜 for 60 seconds (soft bake) to form a photoresist film. The wafer on which the photoresist film was formed was exposed using an ArF exposure apparatus (apparatus name: ASML 1200, manufacturer: ASML) having a numerical aperture of 0.85, and then heated at 95 DEG C for 60 seconds to amplify an acid generated during exposure. (n-butyl acetate) for 60 seconds to form a contact hole pattern having a line width of 110 nm. Three pieces of each of the coating compositions prepared in Examples 1-1 to 1-24 and Comparative Example 1 were coated on the wafer having the contact hole pattern formed thereon, heated at 130 ° C, 140 ° C, and 150 ° C, respectively, (N-butyl acetate) for 60 seconds to develop a fine pattern in which the size (diameter) of the hole was shrunk (a coating film was formed on the pattern). In the case of Comparative Example 2, it was immersed in deionized water (DI) for 60 seconds to be developed. The diameter of the pattern (hole) before forming the coating film and the diameter of the pattern (hole) after formation of the coating film were measured using S-9220 (manufacturer: Hitachi) The amount of change is shown in Table 2 below.

Composition for pattern coating Pattern Diameter (nm) before Coating Film Formation After the formation of the coating film, the pattern diameter (nm) Amount of change in pattern diameter at 150 占 폚 (nm) Change in pattern diameter according to temperature (nm / ° C) 130 ℃ 140 ° C 150 ℃ Example 2-1 Example 1-1 110 95 82 70 40 1.25 Example 2-2 Examples 1-2 112 98 86 73 39 1.25 Example 2-3 Example 1-3 111 95 84 75 36 1.00 Examples 2-4 Examples 1-4 113 92 79 64 49 1.40 Example 2-5 Examples 1-5 108 94 81 65 43 1.45 Examples 2-6 Examples 1-6 111 96 83 68 43 1.40 Examples 2-7 Examples 1-7 110 97 85 74 36 1.15 Examples 2-8 Examples 1-8 110 92 80 65 45 1.35 Examples 2-9 Examples 1-9 112 95 85 70 42 1.25 Examples 2-10 Example 1-10 112 94 81 65 47 1.45 Examples 2-11 Example 1-11 108 94 75 59 49 1.75 Examples 2-12 Examples 1-12 111 81 70 60 51 1.05 Examples 2-13 Examples 1-13 107 95 82 69 38 1.30 Examples 2-14 Examples 1-14 110 97 84 70 40 1.35 Examples 2-15 Examples 1-15 112 86 76 65 47 1.05 Examples 2-16 Examples 1-16 110 89 78 65 45 1.20 Examples 2-17 Examples 1-17 109 95 81 69 40 1.30 Examples 2-18 Example 1-18 108 90 78 63 45 1.35 Example 2-19 Example 1-19 111 86 75 60 51 1.30 Examples 2-20 Examples 1-20 114 87 74 55 59 1.60 Examples 2-21 Examples 1-21 110 85 72 60 50 1.25 Examples 2-22 Examples 1-22 110 84 70 57 53 1.35 Examples 2-23 Examples 1-23 108 79 63 43 65 1.80 Examples 2-24 Examples 1-24 109 101 89 74 35 1.35 Comparative Example 2 Comparative Example 1 111 81 48 0 111 4.05

It can be seen from Table 2 that the composition for photoresist pattern coating developed with the negative tone developer of the present invention is a photoresist pattern (a photoresist pattern developed with a negative tone developer) formed by a method of forming a photoresist pattern using a conventional negative tone developer, It can be seen that the diameter of the hole pattern can be effectively reduced by performing the application (baking) and the developing process on the upper part of the coating layer, and the coating composition having a water-soluble polymer It can be understood that the rate of change of diameter of the hole pattern is stable. Accordingly, when the composition for photoresist pattern coating developed with the negative tone developer of the present invention is applied to the semiconductor production process using the negative tone pattern forming method, the deviation of the diameter (line width (CD)) of the pattern depending on the temperature can be reduced.

Claims (8)

A liposoluble polymer compound having a polarity (log P) of 1.0 to 8.0 and comprising a repeating unit represented by the following formula (1); And
A composition for photoresist pattern coating, which is developed with a negative tone developer comprising an organic solvent having 4 to 12 carbon atoms and containing 1 to 4 oxygen atoms.
[Chemical Formula 1]

Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are each independently a linear hydrocarbon group having 1 to 7 carbon atoms or 1 to 4 carbon atoms or an oxygen atom or a nitrogen atom, And R < ₂ > and R < ₃ > may be connected to each other to form a ring, X is absent, or a linear hydrocarbon group having 1 to 3 carbon atoms Or a branched hydrocarbon group having 3 carbon atoms. [Claim 2] The method according to claim 1, wherein the oil-soluble polymer compound is a polymer compound selected from the group consisting of a homopolymer consisting of only the repeating unit represented by the formula (1), a fat soluble polymer represented by the following formula (2) Composition for coating a photoresist pattern.
(2)

Wherein R ₁ to R ₃ and X are the same as defined in Formula 1, R ₄ is a hydrogen atom or a methyl group, and R ₅ is an alkylene group having 1 to 4 carbon atoms and 1 to 4 carbon atoms and having 1 to 13 carbon atoms A linear hydrocarbon group having 3 to 13 carbon atoms, or a cyclic hydrocarbon group having 3 to 13 carbon atoms, Y is not present, or a linear hydrocarbon group having 1 to 3 carbon atoms or 1 to 3 carbon atoms And a and b are mole% of repeating units constituting the polymer, and each independently is 1 to 99 mol%. [2] The composition of claim 2, wherein the homopolymer comprising only the repeating unit represented by the formula (1) is selected from the group consisting of compounds represented by the following formulas (1a) to (1c) Wherein the compound is selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (I).
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(2i)

(2j)

[Chemical Formula 2k]

≪ EMI ID =

[Formula 2m]

(2n)

(2o)

[Chemical Formula 2p]

[Formula 2q]

In Formulas (2a) to (2q), a and b are the same as defined in Formula (2). The method of claim 1, wherein the organic solvent is selected from the group consisting of n-butyl acetate, diisobutyl ether, n-hexanol, n-heptanol, methyl isobutyl ketone, By weight based on the total weight of the composition. The composition for photoresist pattern coating according to claim 1, wherein the content of the oil-soluble polymer compound is 0.5 to 15% by weight with respect to the composition for a photoresist pattern coating developed with the entire negative tone developer, and the remaining is the organic solvent, A composition for photoresist pattern coating. The photoresist pattern coating composition according to claim 1, wherein the composition for coating a photoresist pattern developed with the negative tone developer further comprises an additive selected from the group consisting of an acid catalyst, a surfactant, a basic compound and a mixture thereof, Is 0.1 to 5 parts by weight based on 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer, and the content of the surfactant is 100 parts by weight of the composition for photoresist pattern coating developed with the entire negative tone developer 0.01 to 5 parts by weight based on 100 parts by weight of the composition for a photoresist pattern coating developed with the entire negative tone developer, 0.01 to 2 parts by weight of the basic compound, A composition for coating a resist pattern. The method of claim 6, wherein the acid catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, benzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, para toluenesulfonic acid, camphorsulfonic acid, Wherein the basic compound is selected from the group consisting of hexylsulfonic acid, acetic acid, ethyl acetic acid, propyl acetic acid, isopropyl acetic acid, and mixtures thereof, and the basic compound is an amine compound. Forming a photoresist film on the semiconductor substrate on which the etching layer is formed;
Exposing the photoresist film to exposure and development with a negative tone developer to form a developed photoresist pattern with a negative tone developer;
Applying a composition for photoresist pattern coating developed with the negative tone developer according to any one of claims 1 to 7 onto a photoresist pattern developed with the negative tone developer; And
And a step of forming a coating film by heating and developing the developed photoresist pattern with a negative tone developing solution coated with the composition for photoresist pattern coating with the negative tone developing solution at 80 to 180 ° C. A method for forming a fine pattern.