KR101789556B1 - Acrylic composition for photoresist fine pattern and method for preparing the composition and method for reducing pattern dimension in photoresist layer using the same - Google Patents

Abstract

The present invention relates to a composition for forming a photoresist fine pattern including a water-soluble polymer composition, a method for producing the same, and a method for forming a photoresist fine pattern using the same, and more particularly, There is provided a composition for forming a photoresist fine pattern which reduces the size of the photoresist pattern by coating the composition for pattern formation on the photoresist pattern, a method for producing the composition, and a method for forming a photoresist fine pattern using the same.
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a composition for forming a photoresist fine pattern including a novel acrylic polymer, a method for producing the same, and a method for forming a photoresist fine pattern using the same. BACKGROUND ART }

The present technology is a technique for providing a water-soluble resin composition containing a novel acrylic polymer for forming a fine pattern and using the resin composition to stably form a fine pattern.

Development of various photoresists has been accelerated due to the high integration and high performance of semiconductor devices and the development of lithography processes. With such high integration and high performance, a chemically amplified photoresist corresponding to the miniaturization of the design rule has been developed together. However, the minimum resolution that can be realized by using the ArF exposure equipment is about 0.05 탆. Accordingly, it is difficult to form a fine pattern for manufacturing integrated semiconductor devices, and various methods have been studied.

As a method of forming a fine pattern widely used up to now, there is a resist thermal reflow method which imparts fluidity by high temperature heat treatment. The size of the contact hole pattern can be reduced by forming a contact hole pattern with a photoresist and then heat-treating the photoresist to a temperature higher than the glass transition temperature. However, according to this method, top-rounding phenomenon and undercut ) Phenomenon may occur, and the adjustment of the critical dimension may be difficult.

Therefore, a technique of coating the functional material on the entire surface of the formed photoresist contact hole and performing a heat treatment on the surface of the formed photoresist contact hole pattern causes a cross-linking reaction at the interface between the functional material and the photoresist contact hole, resulting in reduction of the size of the contact hole pattern It became important. In addition, when the patterning process for patterning by etching using the photoresist pattern coated with the functional material is performed, it must have a property of being able to withstand the etching gas sufficiently.

Therefore, the functional material should satisfy the following requirements.

First, when the functional material is coated on the entire surface of the formed photoresist contact hole, the functional material must be water-soluble since it should not affect the photoresist film and the contact hole pattern and have no reactivity.

Second, a functional material is coated on the entire surface of the formed photoresist contact hole and a heat treatment is performed, so that a cross-linking reaction is required at the interface between the functional material and the photoresist contact hole.

Third, the functional material that has not undergone the crosslinking reaction at a portion other than the interface with the photoresist contact hole should be removed with a water-soluble solvent.

Fourth, since the etching process must be performed using the photoresist pattern coated with the functional material, the resist pattern must be excellent in resistance to etching gas.

On the other hand, a method of reducing the pattern size by using functional materials such as RELACS (manufactured by Clariant) and SAFIER (manufactured by DOKYO KAGAKO CO., LTD.) Is used for the formed photoresist contact hole pattern. However, There is a problem that the process must be repeated several times. In addition, since the functional material does not contain an aromatic structure or a bulky portion, there is a problem that etching resistance is weak when patterning a photoresist pattern coated with a functional material. Furthermore, the above method has a problem that the coating performance against the contact hole pattern, which is becoming increasingly integrated and refined, is insufficient, and the thickness to be crosslinked can not be uniformly controlled according to the heating temperature in the heating process.

Korean Patent No. 1311446 (water-soluble resin composition and method for forming fine pattern using the same)

It is an object of the present invention to provide a composition comprising a novel acrylic water-soluble polymer capable of forming a fine photoresist pattern by effectively reducing the size of a contact hole pattern of a photoresist of a semiconductor process.

Another object of the present invention is to provide a method for producing a polymer composition capable of forming the photoresist fine pattern.

It is still another object of the present invention to provide a method for forming a photoresist fine pattern having a pattern structure having a minute size and a stable shape using the water-soluble resin composition.

In order to solve the above object, a composition for forming a photoresist fine pattern according to an embodiment of the present invention comprises a water-soluble polymer containing a hydrazine group (-NH-NH ₂ ) and a solvent.

The water-soluble polymer containing the hydrazine group may be a water-soluble polymer containing a repeating unit represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

Wherein a is an integer of 0 to 10 and b is an integer of 1 to 4. Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, C _{1 -10} one of which is selected from an alkoxy group, and the group consisting of a cycloalkyl group of C _3-10.)

The water-soluble polymer containing the hydrazine group may be a water-soluble polymer containing a repeating unit represented by the following formula (3).

(3)

Wherein R ₁ to R ₃ are any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The water-soluble polymer containing the hydrazine group may be a water-soluble polymer containing a repeating unit represented by the following formula (4).

[Chemical Formula 4]

(Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. )

The water-soluble polymer containing the hydrazine group may be a water-soluble polymer containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

(Wherein R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. )

The solvent may be any one selected from the group consisting of water, C _1-10 alcohols and C _1-10 alcohols.

The composition for forming a photoresist fine pattern may include 100 parts by weight of the solvent and 0.01 to 0.30 parts by weight of the water-soluble polymer.

The water-soluble polymer may have a weight average molecular weight (Mw) of 1,000 to 10,000 g / mol and a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 0.5 to 3.0.

The water-soluble polymer may further comprise any one of repeating units selected from the following formulas (6) to (8).

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(Wherein c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10. X ^- is an anion of an acid having a pKa of 5 or less And R ₆ to R ₁₁ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.)

According to another embodiment of the present invention, there is provided a process for producing a hydrazine compound, which comprises synthesizing a precursor, reacting the precursor with a hydrazine compound to prepare a water-soluble polymer containing a hydrazine group (-NH-NH ₂ ) (-NH-NH ₂ ), and a solvent, in the presence of a solvent.

The precursor may be a polymer containing a repeating unit represented by the following general formula (9).

[Chemical Formula 9]

(In the formula 9, wherein a is an integer from 0 to 10, wherein b is an integer of 1 to 4. wherein R ₁ to R ₅ are each independently hydrogen, C _1-10 alkyl group, a C _1-10 An alkoxy group, and a C _3-10 cycloalkyl group.

The precursor may be a polymer containing a repeating unit represented by the following formula (10).

[Chemical formula 10]

Wherein R ₁ to R ₃ are any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The precursor may be a polymer containing a repeating unit represented by the following general formula (11).

(11)

(Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. )

The precursor may be a polymer containing a repeating unit represented by the following general formula (12).

[Chemical Formula 12]

(Wherein R ₁ to R ₃ are each independently any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group, , X is any one selected from F, Cl, Br and I.)

The hydrazine compound may be selected from anhydrous hydrazine, hydrazine monohydrate, hydrazine hydrate, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and combinations thereof.

The reaction may be a stirring reaction which proceeds at a temperature of 50 to 150 ° C.

The precursor may further include any one of repeating units selected from the following formulas (6) to (8).

[Chemical Formula 6]

(7)

[Chemical Formula 8]

(Wherein c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10. X ^- is an anion of an acid having a pKa of 5 or less And R ₆ to R ₁₁ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.)

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a photoresist film; Preparing a photoresist pattern film by forming a pattern on the photoresist film by a photolithography process; And coating the photoresist pattern film with the composition for forming a photoresist fine pattern according to any one of claims 1 to 3 on the photoresist pattern film.

The resin composition for forming a fine pattern including a water-soluble polymer and a solvent according to an embodiment of the present invention can form a fine pattern of less than 0.05 mu m in a semiconductor process or the like and minimizes structural defects of a photoresist contact hole such as top rounding and undercut The miniaturization and stability of the semiconductor device including various patterns can be remarkably increased.

According to the method for forming a fine pattern using the water-soluble resin composition according to another embodiment of the present invention, a photoresist fine patterned film having a minute size and a stable shape can be stably and efficiently formed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a method for forming a photoresist fine pattern of the present invention. FIG.

Hereinafter, embodiments of the present invention will be described in detail. It is to be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. .

The composition for photoresist micropatterning according to an embodiment of the present invention comprises a water-soluble polymer and a solvent containing a hydrazine group (-NH-NH ₂ ), and according to another embodiment of the present invention, The size of the pattern can be reduced by coating the composition for forming a fine pattern on the photoresist film.

The water-soluble polymer containing the hydrazine group (-NH-NH ₂ ) may be a water-soluble polymer containing a repeating unit represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

In Formula 1 or Formula 2, a is an integer of 0 to 10, and b is an integer of 1 to 4.

Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The alkyl group, the alkoxy group or the cycloalkyl group may be substituted with hydrogen, an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group, an amine group or an aldehyde group.

The composition for forming a photoresist fine pattern according to another embodiment of the present invention comprises a water-soluble polymer containing a repeating unit represented by the following formula (3) and a solvent, The size of the pattern can be reduced by applying the composition for forming a fine pattern and then coating the composition.

(3)

In Formula 3, R ₁ to R ₃ are each selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

A composition for forming a photoresist fine pattern according to another embodiment of the present invention includes a water-soluble polymer and a solvent containing a repeating unit represented by the following general formula (4) The size of the pattern can be reduced by applying a coating composition for pattern formation and then coating it.

[Chemical Formula 4]

In Formula 4, each of R ₁ and R ₂ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The composition for forming a photoresist fine pattern according to another embodiment of the present invention comprises a water-soluble polymer containing a repeating unit represented by the following formula (5) and a solvent, The size of the pattern can be reduced by applying a coating composition for pattern formation and then coating it.

[Chemical Formula 5]

In Formula 5, R ₁ to R ₃ are each independently any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The water-soluble polymer comprising any one of the repeating units selected from the above formulas (1) to (5) may further comprise at least one repeating unit selected from the following formulas (6) to (8) , Cross-polymerization, block polymerization, graft polymerization, or the like.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 6 to 8, c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10.

Wherein X ^- is an anion of a pKa of 5 or less acid, more specifically, for example, F ^-, Cl ^-, Br ^-, I ^-, such as halide ion, CH ₃ COO ^-, such as acetate ion, SO ₄ ^2-, such as Carbonate ions such as CO ₃ ^2- , nitrate ions such as NO ₃ ^- , hydroxide ions such as OH ^- , and permanganate ions.

Each of R ₆ to R ₁₁ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

Any solvent may be used as long as it can dissolve the water-soluble polymer, and a water-soluble solvent may be preferably used. The water-soluble solvent may be any one selected from the group consisting of an aqueous solution of the alcohol of the water, C _1-10 alkyl-based alcohol, C _1-10 alkoxy-based alcohols and C _1-10 of the alcohol are independently Or may be used as a mixture of two or more.

Preferably, the water-soluble solvent may be an alcohol aqueous solution containing 100 parts by weight of water and 0.1 to 0.30 parts by weight of alcohol. More preferably, the solvent may have an alcohol content of 0.1 to 20 parts by weight, and still more preferably, pure water may be used as the water-soluble solvent.

If the content of the alcohol is less than 0.1 part by weight, the effect of promoting dissolution is deteriorated. If the content of alcohol is more than 30 parts by weight, there is a possibility that the resist height may be reduced by dissolving a small amount of the photoresist pattern .

Examples of the alcohols include alkyl alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol or 2,2-dimethyl- And alkoxy alcohols such as 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 1-methoxy-2-propanol and 3-methoxy-1,2-propanediol. The alcohols may be used alone or in combination of two or more.

The water soluble polymer may be contained in an amount of 0.01 to 0.30 parts by weight based on 100 parts by weight of the solvent, preferably 0.03 to 0.20 parts by weight per 100 parts by weight of the solvent, Can be included. If the water-soluble polymer is contained in an amount of less than 0.01 part by weight, the coating property may deteriorate and the coating film of the photoresist may not be formed. If the water-soluble polymer is contained in excess of 0.30 part by weight, uniformity of the coating may be reduced to cause defects.

The weight average molecular weight (Mw) of the water-soluble polymer is 1,000 to 10,000 g / mol, more preferably 2,000 to 8,000 g / mol, and still more preferably 3,000 to 7,000 g / mol. If the weight average molecular weight of the water-soluble polymer is less than 1,000 g / mol, the pattern shrinkage ratio may be lowered. If the weight average molecular weight is more than 10,000 g / mol, the solubility in a solvent may be lowered. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the water soluble polymer is preferably from 0.5 to 3.0, more preferably from 1.0 to 2.0.

The composition for forming a fine pattern of the present invention may contain water-miscible additives such as crosslinking agents, surfactants, thermal acid generators, photoacid generators, free acids, amines, aminoalcohols, other water-soluble polymers and other additives in addition to the water- / RTI > and / or other solvents.

Some additives include monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-diethanolamine, N-methyldiethanolamine, Amino alcohols such as propylamine, diisopropylamine and triisopropylamine; Amines such as polyalkylenepolyamines, 2-ethylhexylamine, dioctylamine, tripropylamine, tributylamine, triallylamine; And cyclic amines such as piperazine, N-methylpiperazine, and hydroxyethylpiperazine.

In addition, crosslinking agents such as glycoluril, melamine, urea / formamide polymers, and any known crosslinking agents may be used.

Poly (vinylpyrrolidone-co-vinylmalamine), poly (vinylpyrrolidone-co-vinylmalamine), polyvinyl alcohol, partially acetal-capped polyvinyl alcohol, polyallylamine, polyacrylic acid, polymethacrylic acid, And the like may be added to the composition. These polymers may be added in an amount of 0.01 to 0.05 parts by weight.

p-toluenesulfonic acid, perfluorobutanesulfonic acid, perfluorooctanesulfonic acid, (±) camphorsulfonic acid and dodecylbenzenesulfonic acid can be added to the composition.

Any of the known thermal acid generators and photoacid generators which are water-soluble can be used singly or as a mixture. Suitable examples of photosensitive compounds that generate acids include, but are not limited to, ionic photoacid generators (PAGs) such as diazonium salts, iodonium salts, and sulfonium salts. The thermal acid generator (TAG) used in the present invention may be any one that generates an acid capable of cleaving acid-labile bonds present in the present invention upon heating, particularly a strong acid such as sulfonic acid. The thermal acid generator is preferably activated at 90 deg. C, preferably 100 deg. C or higher. The photoresist film is heated for a time length sufficient to react with the resin composition coating film for forming a fine pattern. The free acid, the photoacid generator and / or the thermal acid generator may be incorporated in a range of about 0.1 to 0.05 parts by weight of the entire fine pattern resin composition as a solid.

The composition for forming a photoresist fine pattern according to another embodiment of the present invention includes a step of preparing a precursor, a step of reacting the precursor with a hydrazine compound to form a water-soluble polymer containing a hydrazine group (-NH-NH ₂ ) , And mixing the water-soluble polymer containing the hydrazine group with a solvent to prepare a composition for photoresist fine pattern formation.

According to another embodiment of the present invention, the water-soluble polymer containing the repeating unit represented by the formula (1) or (2) comprises a step of preparing a precursor including a repeating unit represented by the following formula (9) A hydrazine compound is reacted with a precursor containing a repeating unit to be displayed to prepare a water-soluble polymer containing a repeating unit represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

[Chemical Formula 9]

In Formula (1), Formula (2) or Formula (9), a is an integer of 0 to 10, and b is an integer of 1 to 4.

Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

According to another embodiment of the present invention, the water-soluble polymer containing the repeating unit represented by Formula 3 may be prepared by the steps of: preparing a precursor containing a repeating unit represented by Formula 10, And a hydrazine-based compound to prepare a water-soluble polymer containing a repeating unit represented by the following formula (3).

(3)

[Chemical formula 10]

In Formula 3 or Formula 10, R ₁ to R ₃ are any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

According to another embodiment of the present invention, the water-soluble polymer containing the repeating unit represented by the general formula (4) may be prepared by preparing a precursor including a repeating unit represented by the following general formula (11) And a hydrazine-based compound to prepare a water-soluble polymer containing a repeating unit represented by the following formula (4).

[Chemical Formula 4]

(11)

In Formula 4 or Formula 11, R ₁ or R ₂ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. It is one.

According to another embodiment of the present invention, the water-soluble polymer containing the repeating unit represented by the general formula (5) may be prepared by preparing a precursor including a repeating unit represented by the following general formula (12) And a hydrazine-based compound to prepare a water-soluble polymer containing a repeating unit represented by the following formula (5).

[Chemical Formula 5]

[Chemical Formula 12]

In Formula 4 or Formula 12, R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. And X is any one selected from F, Cl, Br and I.

According to another embodiment of the present invention, the precursor containing the repeating units represented by the above formulas (9) to (12) may further comprise one or more repeating units represented by the following formulas (6) to , And the precursors including the repeating units represented by the above formulas (9) to (12) may be copolymerized, cross-polymerized, block-polymerized or graft-polymerized.

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 6 to 8, c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10.

Wherein X ^- is an anion of a pKa of 5 or less acid, more specifically, for example, F ^-, Cl ^-, Br ^-, I ^-, such as halide ion, CH ₃ COO ^-, such as acetate ion, SO ₄ ^2-, such as Carbonate ions such as CO ₃ ^2- , nitrate ions such as NO ₃ ^- , hydroxide ions such as OH ^- , and permanganate ions.

Each of R ₆ to R ₁₁ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.

The reaction between the hydrazine compound and the precursor containing the repeating units represented by the above Chemical Formulas 9 to 12 is performed by reacting 10 to 30 parts by weight of the hydrazine compound per 100 parts by weight of the precursor containing the repeating units represented by Chemical Formulas 9 to 12 And the reaction temperature is preferably in the range of 50 to 150 ° C.

If the hydrazine compound is contained in an amount of less than 10 parts by weight, the substitution reaction may not be completed. On the other hand, if it exceeds 30 parts by weight, it may be difficult to obtain a precipitate.

If the reaction temperature is lower than 50 ° C, the reaction time may be very long. If the reaction temperature is higher than 150 ° C, it is difficult to control the side reaction.

Examples of the polymers of the above Chemical Formulas (1) to (12) include copolymers represented by the following Chemical Formulas (13) to (16).

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

[Chemical Formula 16]

Wherein a and b are the molar ratios of the respective repeating units, a is a real number of 0.01 to 1, b is a real number of 0 to 0.99, and a + b = 1.

And e is an integer of 1 to 3.

The polymer containing the repeating units represented by the above formulas (1) to (16) may be a block copolymer, a random copolymer, or a graft copolymer. The polymers may be polymerized by a conventional method, but particularly preferred may be prepared by a secondary reaction with hydrazine after the primary polymerization is carried out by radical polymerization.

Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), lauryl peroxide, azobisisocapronitrile, azobisisobalonitrile, and t-butyl hydroperoxide And the kind of the radical polymerization initiator is not particularly limited.

As the polymerization method, bulk polymerization, solution polymerization, suspension polymerization, bulk suspension polymerization, emulsion polymerization and the like can be used.

As the polymerization solvent, benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran, esters, ethers, lactones, ketones, amides and alcohols can be used. Or may be used as two or more mixed solvents.

The polymerization temperature is appropriately selected depending on the kind of the catalyst. The molecular weight distribution of the polymer can be appropriately controlled by changing the amount of the polymerization initiator used and the reaction time. Unreacted monomers and by-products remaining in the reaction mixture after completion of the polymerization can be removed by a precipitation method using a solvent.

The precipitation solvent may be a saturated hydrocarbon, an unsaturated hydrocarbon, an alcohol, an ether, an ester, a ketone, a carboxylic acid, an aldehyde or the like, and the precipitation solvent may be used singly or in combination of two or more.

After the polymer by the first polymerization reaction is formed, the second reaction may proceed by adding the hydrazine compound. The hydrazine compound may be selected from anhydrous hydrazine, hydrazine monohydrate, hydrazine hydrate, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and combinations thereof.

As the reaction solvent used in the second reaction, benzene, toluene, xylene, halogenated benzene, diethyl ether, tetrahydrofuran, esters, ethers, lactones, ketones, amides and alcohols can be used. The solvent may be used alone or in combination of two or more.

The reaction temperature is 50 to 150 캜. The reaction may be carried out by stirring, and any of reflux stirring, gas injection stirring, cooling stirring, heating stirring, constant temperature stirring, continuous stirring, and non-continuous stirring may be used.

After the completion of the second reaction, ketones, aldehydes, ethers, esters, and alcohols are added to the reaction mixture to terminate the reaction, followed by washing, filtration, and drying. Finally, A water-soluble resin polymer can be obtained.

The water-soluble resin polymer prepared by the above primary and secondary reactions can be mixed with an appropriate solvent to prepare a water-soluble resin composition for forming a fine pattern. The kind and mixing ratio of the solvent are as described above.

According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a photoresist film; Preparing a photoresist pattern film by forming a pattern on the photoresist film by a photolithography process; And coating the photoresist pattern film with a composition for forming a fine pattern including the water-soluble polymer of claim 1.

A method of forming a photoresist fine pattern of the present invention will be described with reference to FIG.

The fine patterned photoresist thin film 10 is formed by first applying a photoresist composition 110 on a wafer substrate 100 and then drying to form a film. Followed by a heat treatment using a laser stepper, followed by a heat treatment, and development, washing, and drying with a tetramethylammonium hydroxide aqueous solution to form a photoresist pattern. The photoresist pattern may be a contact hole pattern, but the present invention is not limited thereto.

A third step of applying the resin composition 120 for forming a fine pattern described above on the photoresist pattern film 110 including a plurality of contact holes formed by the above method and drying to form a film.

The step of coating the composition for forming a fine pattern including the water-soluble polymer on the photoresist pattern may be any method of forming a coating layer. A step of selectively applying a composition for forming a fine pattern including the water-soluble polymer on the photoresist pattern film, a step of bringing a part of the composition for forming a fine pattern into contact with the photoresist pattern film, And removing the unreacted portion of the composition for forming a fine pattern with the removing solution in the reaction step, but the present invention is not limited thereto.

The heat treatment (photoresist baking) reaction may be performed at a temperature of 50 to 200 ° C, preferably at a temperature of 80 to 200 ° C. When the heat treatment temperature is lower than 50 캜, the crosslinking reaction may not be smoothly performed. On the other hand, when the heat treatment temperature exceeds 200 캜, deterioration and defects of the photoresist pattern may be caused.

The removing solution may be any one selected from the group consisting of water, a C _1-30 alcohol and an aqueous solution obtained by mixing water and C _1-30 alcohol, and the solvent and the removing solution contained in the resin composition for forming a fine pattern May be the same or different.

By varying the heat treatment temperature and the resin composition, the thickness of the crosslinked film can be controlled, and the size of the contact hole can be controlled by adjusting the thickness of the crosslinked film.

Hereinafter, the water-soluble resin composition of the present invention will be described in more detail with specific polymerization and examples. However, the technical idea of the present invention is not limited by the following embodiments.

Polymerization Example  One

60 g of γ-butyrolactone methacrylate and 9 g of hydroxyadamantane methacrylate are added to a 500 ml round-bottomed flask and 175 ml of methyl ethyl ketone is added to dissolve. After 5.4 g of the initiator was dissolved therein, the temperature of the reactor was raised to 70 캜 and stirred for 3 hours. The resulting polymerization solution was cooled to room temperature, and then the reaction solution was slowly added dropwise to the precipitating solvent n-heptane to be precipitated. The resultant precipitate was filtered with a reduced pressure filter, and dried under reduced pressure for 12 hours to obtain 51 g of a polymer containing a repeating unit represented by the formula (17) (yield: 74%). The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 6,155, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.46.

[Chemical Formula 17]

Polymerization Example  2

78 g of norbornane carbolactone methacrylate and 9 g of hydroxyadamantane methacrylate are added to a 500 ml round bottom flask and 260 ml of methyl ethyl ketone is added to dissolve. After 5.4 g of the initiator was dissolved therein, the temperature of the reactor was raised to 70 캜 and stirred for 3 hours. The resulting polymerization solution was cooled to room temperature, and then the reaction solution was slowly added dropwise to the precipitating solvent n-heptane to be precipitated. The resulting precipitate was filtered with a reduced pressure filter and then dried under reduced pressure for 12 hours to obtain 65 g of a polymer containing a repeating unit represented by the formula (18) (yield: 74%). The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 4,941, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.87.

[Chemical Formula 18]

Polymerization Example  3

60 g of γ-butyrolactone methacrylate is added to a 500 ml round bottom flask and 180 ml of methyl ethyl ketone is added to dissolve. After dissolving 5.0 g of the initiator therein, the temperature of the reactor was raised to 70 캜 and stirred for 3 hours. The resulting polymerization solution was cooled to room temperature, and then the reaction solution was slowly added dropwise to the precipitating solvent diisopropyl ether to precipitate. The resulting precipitate was filtered with a reduced pressure filter, and dried under reduced pressure for 12 hours to obtain 42 g of a polymer containing a repeating unit represented by the formula (19) (yield: 70%). The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 6,603, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.56.

[Chemical Formula 19]

Polymerization Example  4

In a 500 ml round-bottom flask, add 78 g of norbornane carbolactone methacrylate and 234 ml of methyl ethyl ketone to dissolve. After dissolving 5.0 g of the initiator therein, the temperature of the reactor was raised to 70 캜 and stirred for 3 hours. The resulting polymerization solution was cooled to room temperature, and then the reaction solution was slowly added dropwise to the precipitating solvent diisopropyl ether to precipitate. The resulting precipitate was filtered with a reduced pressure filter, and then dried under reduced pressure for 12 hours to obtain 62 g of a polymer containing recurring units of formula (20) (yield: 79%). The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer was 3,556, and the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight was 1.51.

[Chemical Formula 20]

Reaction Example  One

30 g of the polymer obtained in Polymerization Example 1 was dissolved in 90 ml of methyl ethyl ketone, 6 g of hydrazine monohydrate was added, and the mixture was refluxed and stirred at 90 ° C for 3 hours. After the reaction, the resulting compound is dissolved in acetone and stirred. After stirring for 1 hour, the resulting polymer is filtered under reduced pressure, filtered and dried under reduced pressure at 50 ° C for 6 hours. The structure of the obtained compound was confirmed by < 1 > H NMR and can be represented by formula (21).

^{1 H-NMR (DMSO-D6} ): (ppm) 0.6 ~ 1.2 (br, 5.4H), 1.4 ~ 2.2 (br, 2.8H), 3.4 ~ 4.6 (br, 4.6H), 4.8 (br, 0.9H) , 8.8-9.0 (br, 0.9H), 9.2-9.5 (br, 0.9H)

[Chemical Formula 21]

Reaction Example  2

25 g of the polymer obtained in Polymerization Example 3 was dissolved in 75 ml of methyl ethyl ketone, and then 5.5 g of hydrazine monohydrate was added thereto, followed by reflux and stirring at 90 ° C for 3 hours. After the reaction, the resulting compound is dissolved in acetone and stirred. After stirring for 1 hour, the resulting polymer is filtered under reduced pressure, filtered and dried under reduced pressure at 50 ° C for 6 hours. The structure of the obtained compound was confirmed by < 1 > H NMR and can be represented by formula (22).

^{1 H-NMR (DMSO-D6} ): (ppm) 0.8 ~ 1.2 (br, 4H), 1.4 ~ 2.0 (br, 3H), 3.6 ~ 4.6 (br, 4H), 4.8 (br, 1H), 8.8 ~ 9.1 (br, IH), 9.2-9.4 (br, IH)

[Chemical Formula 22]

Reaction Example  3

25 g of the polymer obtained in Polymerization Example 4 was dissolved in 75 ml of methyl ethyl ketone, and then 6.5 g of hydrazine monohydrate was added thereto, followed by reflux and stirring at 90 ° C for 3 hours. After the reaction, the resulting compound is dissolved in acetone and stirred. After stirring for 1 hour, the resulting polymer is filtered under reduced pressure, filtered and dried under reduced pressure at 50 ° C for 6 hours. The structure of the obtained compound was confirmed by < 1 > H NMR and can be represented by formula (23).

^{1 H-NMR (DMSO-D6} ): (ppm) 0.5 ~ 1.1 (br, 8H), 1.5 ~ 2.2 (br, 3H), 3.5 ~ 4.4 (br, 4H), 4.7 (br, 1H), 8.8 ~ 9.1 (br, IH), 9.2-9.4 (br, IH)

(23)

[ Photoresist  Method for producing fine pattern]

Example  One

On the silicon wafer substrate, a photoresist composition was applied to the substrate using a spinner and dried at 110 DEG C for 90 seconds to form a film having a thickness of 0.2 mu m. The formed film was exposed using an ArF excimer laser stepper (lens numerical aperture: 0.78), and then heat-treated at 110 DEG C for 90 seconds. Then, the resist was developed, washed and dried in a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 40 seconds to form a resist pattern. At this time, the width (CD ₀ ) value of the resist pattern is measured.

Resin composition 1 for fine pattern formation containing 100 parts by weight of isopropyl alcohol aqueous solution (1 part by weight of isopropyl alcohol per 100 parts by weight of water) containing 0.20 parts by weight of a compound containing a repeating unit represented by formula (21) in Reaction Example 1 was prepared.

The fine pattern-forming resin composition 1 was spin-coated on the formed photoresist pattern film and heat-treated at 110 ° C for 60 seconds to coat the photoresist pattern film on the adjacent photoresist pattern film, and the width (CD) value of the fine pattern was measured .

Example  2

The procedure of Example 1 was repeated, except that a compound containing a repeating unit represented by Chemical Formula 22 in Reaction Example 2 was used in the resin composition for forming a fine pattern.

Example  3

The procedure of Example 1 was repeated except that a compound containing a repeating unit represented by the formula (23) in Reaction Example 3 was used in the resin composition for forming a fine pattern.

Comparative Example  One

The procedure of Example 1 was repeated except that a compound containing a repeating unit represented by the following formula (24) was used in the resin composition for forming a fine pattern.

≪ EMI ID =

Comparative Example  2

The procedure of Example 1 was repeated, except that a compound containing a repeating unit represented by the following formula (25) was used in the resin composition for forming a fine pattern.

(25)

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Before coating CD ₀ (탆) 0.0920 0.0921 0.0918 0.0921 0.0923 After coating, the CD (탆) 0.0802 0.0789 0.0788 0.0822 0.0821

When Examples 1 to 3 and Comparative Examples 1 to 2 were compared, in the case of Examples 1 to 3 containing the compound of the present invention, the difference in pattern interval was larger when compared before and after coating, It can be seen that a fine interval pattern can be obtained.

10: Photoresist fine pattern film
100: substrate
110: Photoresist composition and photoresist film
120: composition for forming fine pattern coating film

Claims (18)

A water-soluble polymer comprising a hydrazine group (-NH-NH ₂ ) and a solvent,
Wherein the water-soluble polymer containing the hydrazine group is a water-soluble polymer containing a repeating unit represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

Wherein a is an integer of 0 to 10 and b is an integer of 1 to 4. Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, C _{1 -10} one of which is selected from an alkoxy group, and the group consisting of a cycloalkyl group of C _3-10.)
delete A water-soluble polymer comprising a hydrazine group (-NH-NH ₂ ) and a solvent,
Wherein the water-soluble polymer containing the hydrazine group is a water-soluble polymer containing a repeating unit represented by the following formula (3).
(3)

Wherein R ₁ to R ₃ are any one selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.
A water-soluble polymer comprising a hydrazine group (-NH-NH ₂ ) and a solvent,
Wherein the water-soluble polymer containing the hydrazine group is a water-soluble polymer containing a repeating unit represented by the following formula (4).
[Chemical Formula 4]

(Wherein R ₁ and R ₂ are each independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group. )
delete 5. The method according to any one of claims 1 to 4,
_Wherein the solvent is any one selected from the group consisting of water, a C _1-10 alcohol, and an aqueous C _1-10 alcohol solution.
5. The method according to any one of claims 1 to 4,
Wherein the composition for forming a photoresist fine pattern comprises 100 parts by weight of the solvent and 0.01 to 0.30 parts by weight of the water-soluble polymer.
5. The method according to any one of claims 1 to 4,
Wherein the water-soluble polymer has a weight average molecular weight (Mw) of 1,000 to 10,000 g / mol and a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 0.5 to 3.0.
5. The method according to any one of claims 1 to 4,
Wherein the water-soluble polymer further comprises any one of recurring units selected from recurring units of the following formulas (6) to (8) and recurring units of two or more of the following formulas Composition.
[Chemical Formula 6]

(7)

[Chemical Formula 8]

Wherein c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10. X ^- represents a halogen ion, an acetate ion, a sulfide Wherein each of R ₆ to R ₁₁ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkyl group, a C _1-10 alkoxy group, An alkoxy group, and a C _3-10 cycloalkyl group.
Synthesizing a precursor,
Reacting the precursor with a hydrazine-based compound to prepare a water-soluble polymer containing a hydrazine group (-NH-NH ₂ ), and
Mixing a water-soluble polymer comprising the hydrazine group (-NH-NH ₂ ) with a solvent,
Wherein the precursor comprises any polymer selected from repeating units represented by the following general formulas (9) to (11).
[Chemical Formula 9]

[Chemical formula 10]

(11)

(In the above formulas 9 to 11,
A is an integer of 0 to 10, b is an integer of 1 to 4,
Each of R ₁ to R ₅ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkoxy group, and a C _3-10 cycloalkyl group.
delete delete delete delete 11. The method of claim 10,
Wherein the hydrazine compound is selected from the group consisting of anhydrous hydrazine, hydrazine monohydrate, hydrazine hydrate, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and combinations thereof. Gt;
11. The method of claim 10,
Wherein the reaction is a stirring reaction proceeding at a temperature of 50 to 150 占 폚.
11. The method of claim 10,
Wherein the precursor further comprises a repeating unit selected from the group consisting of repeating units represented by the following formulas (6) to (8) and repeating units represented by the following formulas (6) to ≪ / RTI >
[Chemical Formula 6]

(7)

[Chemical Formula 8]

Wherein c is an integer of 1 to 3, p is an integer of 0 to 20, and q is an integer of 1 to 10. X ^- represents a halogen ion, an acetate ion, a sulfide Wherein each of R ₆ to R ₁₁ is independently selected from the group consisting of hydrogen, a C _1-10 alkyl group, a C _1-10 alkyl group, a C _1-10 alkoxy group, An alkoxy group, and a C _3-10 cycloalkyl group.
Forming a photoresist film;
Preparing a photoresist pattern film by forming a pattern on the photoresist film by a photolithography process;
Coating a composition for forming a photoresist fine pattern according to any one of claims 1 to 3 on the photoresist pattern film.

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