KR100737851B1 - Micropattern forming resin composition and method for forming micropattern using thereof - Google Patents

Abstract

Provided is a resin composition for forming a micropattern, which reduces the area or interval in an engraved portion of a photoresist layer during a semiconductor lithography process, and allows formation of a fine pattern beyond a wavelength limit. The resin composition(4) for forming a micropattern by being coated on a photoresist pattern layer comprises an aqueous solution containing an alcohol or alkali, and a water soluble polymer. The resin composition causes surface swelling of the photoresist pattern layer(3) or formation of entanglement between the photoresist pattern layer(3) and the water soluble polymer. Particularly, the water soluble polymer includes a homopolymer comprising hydrophilic monomer units or a copolymer of at least two hydrophilic monomer units. The resin composition comprises 50-99 wt% of the alcohol- or alkali-containing aqueous solution and 1-50 wt% of the water soluble polymer.

Description

Micropattern forming resin composition and method for forming micropattern using pretty}

1 is a conceptual diagram for explaining the steps of forming a fine pattern by applying the resin composition for forming a micropattern of the present invention on the surface of a resist pattern layer in order.

※ Explanation of codes for main parts of drawing

1: Substrate 2: Photoresist Resin Layer

3: Resist pattern layer 4: Coating layer of resin composition for fine pattern formation

5: swelled resist pattern layer 6: layer in which entanglement has occurred

The present invention relates to a resin composition for forming a micropattern capable of reducing the area to the spacing of the intaglio portion in a semiconductor lithography process.

Recently, as semiconductor devices have been increasingly integrated, wiring and isolation widths required in the manufacturing process have become very fine. In general, the process required for semiconductor device development is largely composed of lithography, etching, cleaning, ion implantation, thin film formation, metallization process, etc. Among them, the pattern forming technology of the lithography process is the core, which serves as a driving force for ultra-high integration of semiconductors. Doing

Typical lithographic processes involve forming a patterned resist layer by patterning exposing the radiation-sensitive resist to imaging radiation. The image is then developed by contacting the exposed resist layer with any material (typically an aqueous alkaline developer). The pattern is then transferred to the backing material by etching the material in the openings of the patterned resist layer. After the transfer is completed, the remaining resist layer is removed.

      The lithographic technique requires both shortening the exposure light and developing a resist material having a high resolution in accordance with the characteristics of the light. However, in order to shorten the wavelength of the exposure light, improvement of the exposure apparatus is required, and enormous cost is required. On the other hand, development of a resist material corresponding to exposure light of short wavelength is not easy.

In particular, in the conventional lithography technology, there is a limit in improving the degree of integration through the pattern miniaturization due to the limitation of the exposure wavelength with respect to the pattern miniaturization. In an attempt to overcome this limitation, in Japanese Patent No. 3071401 and the like, a non-crosslinking film is formed by forming a crosslinked film in a portion in contact with a resist pattern by an acid provided from a resist pattern using a water-soluble resin that crosslinks with a resist in the presence of an acid. Micropattern forming materials have been introduced, characterized in that the parts are peeled off.

However, when the pattern is formed using the material, there is a problem that the resist pattern is deformed due to internal stress generated by the volume shrinkage of the resin during the crosslinking reaction. Therefore, the need for the development of the micro pattern forming material of the new mechanism that overcomes the limitation of the existing material has been raised.

The present invention is to provide a fine pattern forming material of a novel mechanism capable of forming a fine pattern beyond the wavelength limit in miniaturization of separation patterns, hole patterns and the like by overcoming the problems of the prior art.

The present inventors induce swelling of the photoresist pattern layer using an alcohol or alkali aqueous solution to solve the above technical problem, and when the entanglement between the swelled photoresist pattern layer and the water-soluble polymer is generated, the intaglio of the photoresist pattern layer It has been found that the spacing of the parts can be made fine, thus completing the present invention.

 The present invention provides a resin composition for forming a micropattern, wherein the resin composition for forming a micropattern coated on the photoresist pattern layer comprises an aqueous solution containing an alcohol or an alkali and a water-soluble polymer.

     The water-soluble polymer may be a homopolymer consisting of hydrophilic monomer units or a copolymer between two or more hydrophilic monomer units.

The water-soluble polymer may include at least one hydrophilic monomer unit, vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole, and vinyl tetra It may be a copolymer composed of at least one monomer unit selected from the group consisting of imidazole.

The water-soluble polymer may be a copolymer comprising at least one hydrophilic monomer unit and at least one (meth) acrylic monomer unit containing a functional group selected from the group consisting of adamantyl, tricyclodecanyl, norbornyl, and isobornyl groups. have.

The hydrophilic monomer unit of the water-soluble polymer may include one or two or more functional groups selected from the group consisting of hydroxyl group, carboxylic acid group, amide group, amine group, heterocyclic group, ether group, ester group, acetal group and sulfonic acid group. have.

The hydrophilic monomer unit of the water-soluble polymer is vinyl alcohol, vinyl carbohydrate, acrylic acid, methacrylic acid, ethylene oxide, vinyl hydroxyethyl methacrylate, benzoacrylic acid, vinylpyrrolidone, vinylamine, allylamine, vinylimidazole And vinyloxazoline.

Vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole, vinyl tetraimida to the hydrophilic monomer unit number of the water-soluble polymer. The ratio of the number of monomer units selected from the group consisting of sol may be 0.01 to 0.5.

The ratio of the number of (meth) acryl monomer units containing a functional group selected from the group consisting of adamantyl group, tricyclodecanyl group, norbornyl group, and isobonyl group with respect to the hydrophilic monomer unit number of the water-soluble polymer may be 0.01 to 0.5. .

      The water-soluble polymer may have a weight average molecular weight (Mw) of 5,000 ~ 1,000,000.

The alcohol may be at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol, and hydrobenzoin.

The alkali may be an organic amine or an ammonium hydroxide.

The alkali is 2- (2-aminoethylamino) ethanol, 1,1,3,3-tetrakis (methoxymethyl) urea, ethylenediamine, diethylenetriamine, pyridine, allylamine, aminoethanol and triethylamine One or more may be selected from the group consisting of.

The resin composition for forming a micropattern may include 50 to 99% by weight of an aqueous solution containing alcohol or alkali and 1 to 50% by weight of a water-soluble polymer.

The alcohol or alkali may be contained 0.1 to 5 parts by weight based on 100 parts by weight of water.

      In addition, the present invention comprises the steps of: a) forming a photoresist resin layer on the substrate; b) exposing and developing the photoresist resin layer to form a photoresist pattern layer; c) applying the resin composition for forming a micropattern of the present invention on the surface of the photoresist pattern layer; d) swelling on the surface of the photoresist pattern layer to form a swollen photoresist pattern layer; e) entangling between the swollen photoresist pattern layer portion and the water-soluble polymer of the resin composition for forming a micropattern; And f) removing the water-soluble polymer portion except for the portion in which the entanglement has occurred with water, an aqueous alkali solution or an aqueous solution containing an organic solvent.

      In addition, the present invention provides a semiconductor integrated circuit device, characterized in that formed by the fine pattern forming method.

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

The resin composition for forming a micropattern of the present invention is a resin composition for forming a micropattern coated on a photoresist pattern layer, and includes an aqueous solution containing an alcohol or an alkali and a water-soluble polymer.

In the resin composition for forming a micropattern of the present invention, an aqueous solution containing an alcohol or an alkali causes swelling on the surface of the photoresist pattern layer, and the water-soluble polymer on the surface and the adjacent portion of the photoresist pattern layer swells the photoresist pattern. The insoluble film portion is formed by causing the layer portion and the entanglement. Accordingly, the portion not formed of the entanglement is characterized by being removed by an aqueous solution containing water or an alkaline aqueous solution or an organic solvent used as a developer.

 The water-soluble polymer is a copolymer comprising a homopolymer or a hydrophilic monomer unit consisting of hydrophilic monomer units.

The hydrophilic monomer unit of the water-soluble polymer includes one or two or more functional groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, an amide group, an amine group, a heterocyclic group, an ether group, an ester group, an acetal group and a sulfonic acid group. desirable. More specifically, vinyl alcohol, vinyl carbohydrate, vinyl hydroxyethyl methacrylate, etc. can be used as a monomer containing a hydroxyl group, and acrylic acid, methacrylic acid, benzoacrylic acid etc. can be used as a monomer containing a carboxylic acid group. As the monomer containing an amine group, vinylamine, allylamine, etc. may be used, and as the monomer containing a heterocyclic group, monomers such as vinylpyrrolidone, vinyloxazoline, and vinylimidazole may be used. Ethylene oxide can also be used.

As said water-soluble polymer, the homopolymer which used each of said hydrophilic monomeric units may be used independently, and the copolymer obtained by combining two or more types of these can also be used.

In addition, as the water-soluble polymer, a copolymer made of at least one hydrophilic monomer unit and a monomer unit having affinity with a resin forming a photoresist pattern may be used. In this case, the monomer unit having affinity with the resin constituting the photoresist pattern may be selected according to the type of photoresist pattern layer applied.

As a specific example, when the applied photoresist pattern layer is KrF photoresist including polyhydroxy styrene, the monomer unit having affinity with the resin constituting the photoresist pattern may include vinylpyridine, vinylthiophene, styrene, and vinyl carba. It is preferred to use one or more selected from the group consisting of sol, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinyltetriimidazole.

In addition, when the applied photoresist pattern layer is an ArF photoresist including an alicyclic ring structure, the monomer unit having affinity with the resin constituting the photoresist pattern may be an adamantyl group, tricyclodecanyl group, norbornyl group or iso It is preferable to select and use 1 or more types of (meth) acryl monomers containing the functional group chosen from the group which consists of a carbonyl group.

When using a copolymer made of a monomer unit having affinity with the resin forming the photoresist pattern and the hydrophilic monomer unit as the water-soluble polymer, the monomer unit having affinity with the resin forming the photoresist pattern with the hydrophilic monomer unit The copolymerized in various patterns can be used within the range that does not harm, and random copolymers, block copolymers, and graft copolymers can be used, but random copolymers are preferable.

When using the copolymer which consists of a monomer unit which has affinity with the resin which comprises the said hydrophilic monomer unit and a photoresist pattern as said water-soluble polymer, the ratio of the number of monomer units which have an affinity with resin which comprises a photoresist pattern with respect to a hydrophilic monomer unit number It is preferable to use the copolymer which is 0.01-0.5. If less than 0.01, the entanglement phenomenon with the photoresist resin does not occur well, and if it exceeds 0.5, there is a problem that may damage the water solubility.

The molecular weight of the water-soluble polymer may be arbitrarily selected within a range that does not impair the effects of the present invention, but in order to maximize the effect of entangling with the photoresist resin after application while ensuring effective water solubility and applicability, the weight average molecular weight (Mw) It is preferable that it is 5,000-1,000,000. More preferably, the weight average molecular weight is 30,000 to 100,000. If the weight average molecular weight is less than 5,000, the entanglement between the water-soluble polymer and the swollen photoresist resin is insufficient, if the weight average molecular weight exceeds 1,000,000, the water solubility is lowered and agglomeration may occur due to uneven coating.

The polymer for forming the resist pattern layer may be any general photosensitive resin. For example, in the case of KrF photoresist, a part of hydroxy group of polyhydroxystyrene is substituted with ethylenevinylether, which is an acid-sensitive protecting group, and in the case of ArF photoresist, An organic polymer which is insoluble in water as a form in which an acid-sensitive protecting group is substituted in an alicyclic ring structure may be mentioned.

In both cases, the polymer on the patterned surface is in a state in which a part of the protecting group is desorbed, and the polymer in this state may be dissolved in a high concentration of an alcohol or alkali aqueous solution. The photoresist pattern layer can be adjusted to the extent that only the surface swells without being completely dissolved.

In addition to controlling the degree of swelling by adjusting the alcohol or alkali content, by adjusting the molecular weight of the water-soluble polymer, it is possible to adjust the degree of ingotation and insolubilization to reduce the distance between the patterns or the size of the hole opening. . For example, in one embodiment of the present invention described below, a water-soluble polymer having a weight average molecular weight of about 70 K was used to obtain a reduction in the interval of the intaglio portion of the photoresist pattern layer of about 40 nm.

The water-soluble resin composition of this invention contains the aqueous solution containing alcohol or alkali. Since the alcohol or alkali aqueous solution penetrates the surface of the photoresist pattern layer resin and serves to swell the resin, the alcohol and alkali are not particularly limited except that the alcohol and the alkali should be water-soluble.

As the alcohol in the aqueous solution, for example, alkyl alcohol, allyl alcohol, etc. may be used as the water-soluble alcohol, and specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol and hydrobenzoin It is preferable to use any one or more selected from the group.

As the alkali, organic amines such as alkylamine, benzoamine, diamine or ammonium hydroxide can be used, and more specifically, 2- (2-aminoethylamino) ethanol (2- (2- aminoethylamino) ethanol), 1,1,3,3-tetrakis (methoxymethyl) urea (1,1,3,3-tetrakis (methoxymethyl) urea) represented by the following formula (2), ethylenediamine, diethylenetriamine Preference is given to using at least one selected from the group consisting of pyridine, allylamine, aminoethanol and triethylamine.

[Formula 1]

[Formula 2]

In the present invention, the resin composition for forming a micropattern is preferably made of 50 to 99% by weight of an aqueous solution containing alcohol or alkali and 1 to 50% by weight of a water-soluble polymer. When the content of the water-soluble polymer is less than 1% by weight, the effect of entanglement with the photoresist resin is insufficient, and when the content of the water-soluble polymer exceeds 50% by weight, the coating property is poor when the resin composition for forming the micropattern is coated on the surface of the photoresist pattern layer. The problem arises.

In addition, the alcohol or alkali in the aqueous solution is preferably contained in 0.1 to 5 parts by weight, more preferably 0.5 to 1 part by weight based on 100 parts by weight of water. When the content is less than 0.1 part by weight, the swelling of the photoresist pattern layer resin does not occur satisfactorily, and when used in excess of 5 parts by weight, the pattern may be collapsed due to the dissolution of the photoresist pattern layer resin.

  In the present invention, a) forming a photoresist resin layer on the substrate; b) exposing and developing the photoresist resin layer to form a photoresist pattern layer; c) applying the resin composition for forming a micropattern of the present invention on the surface of the photoresist pattern layer; d) swelling on the surface of the photoresist pattern layer to form a swollen photoresist pattern layer; e) entangling between the swollen photoresist pattern layer portion and the water-soluble polymer of the resin composition for forming a micropattern; And f) removing the remaining water-soluble polymer portion except for the portion where the entanglement has occurred with an aqueous solution including water, an aqueous alkali solution or an organic solvent.

The method of forming a fine pattern according to the present invention will be described in detail below with reference to FIG. 1 as an example in which a fine pattern is formed by a KrF resist.

(A) -f) of FIG. 1 is a step of forming a fine pattern by applying the resin composition for forming a micropattern of the present invention on the surface of the KrF resist pattern layer, causing swelling in the resist pattern layer resin and causing entanglement to occur. This is a conceptual diagram for explaining.

As shown in Fig. 1A), for example, a KrF resist resin layer 2 is formed on a substrate 1 such as a semiconductor substrate. Thereafter, a KrF excimer laser light source is irradiated using a photomask (not shown), the photoresist resin layer 2 is exposed, and then developed to form a resist pattern layer 3 (FIG. 1B). Next, as shown in Fig. 1C), the resin pattern for forming a micropattern according to the present invention is applied to the resist pattern layer 3 to form a coating layer 4 of the resin composition for forming a micropattern. The swelling phenomenon occurs on the surface of the resist pattern layer 3 by the alcohol or alkaline aqueous solution component of the coating layer 4 thus formed, thereby forming a swollen resist pattern layer 5 (FIG. 1D)). At this time, the layer 6 in which the swelled photoresist pattern layer 5 and the water-soluble polymer chain of the micropattern-forming resin composition are entangled and entangled at the site of contact with the coating layer 4 of the micropattern-forming resin composition. (FIG. 1 e)). Subsequently, the coating layer 4 of the resin composition for forming a micropattern without entanglement phenomenon is removed by using water or an aqueous alkali solution or an aqueous solution containing an organic solvent, thereby minimizing the interval CD _A of the intaglio portion of the photoresist pattern layer. One fine pattern can be implemented (FIG. 1 f)).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Synthesis Example 1 (Synthesis of Water-Soluble Polymer 1 (Mw = 5K))

300 ml of isopropyl alcohol was added to a 500 ml three-necked flask, and the mixture was stirred under nitrogen atmosphere for 1 hour and heated to reflux at 70 ° C. 71.94 g of N-vinylpyrrolidone, 13.60 g of 4-vinylpyridine, 2.56 g of dimethyl-2,2'-azobis-2-methylpropio Nate (dimethyl-2,2'-azobis-2-methylpropionate) and 50 ml of isopropyl alcohol were added and stirred for 4 hours. After cooling the solution to room temperature, the solution was concentrated by evaporation to 1/2 or less using a vacuum distillation apparatus, and then precipitated by adding 500 ml of diethyl ether. The precipitate was filtered, washed with diethyl ether, and purified three times, and dried in an oven, followed by drying in an oven (poly (vinylpyrrolidone-co-vinylpyridine) represented by Formula 3 below. )) 80.53 g of copolymer were obtained. The weight average molecular weight of the obtained copolymer was 5K, and the ratio of m / n was 0.2.

[Formula 3]

Synthesis Example 2 (Synthesis of Water-Soluble Polymer 2 (Mw = 10K))

Using the same method as in Synthesis Example 1, except that 1.5 g of dimethyl-2,2'-azobis-2-methylpropionate, an initiator, was used 80.53 g of a poly (vinylpyrrolidone-co-vinylpyridine) copolymer having an average molecular weight of 10 K was obtained.

Synthesis Example 3 (Synthesis of Water-Soluble Polymer 3 (Mw = 20K))

Using the same method as in Synthesis Example 1, except that 0.7 g of dimethyl-2,2'-azobis-2-methylpropionate, an initiator, was used 70.70 g of a poly (vinylpyrrolidone-co-vinylpyridine) copolymer having an average molecular weight of 20K was obtained.

Synthesis Example 4 (Synthesis of Water-Soluble Polymer 4 (Mw = 70K))

Using the same method as in Synthesis Example 1, except that 0.2 g of dimethyl-2,2'-azobis-2-methylpropionate, an initiator, was used. 78.43 g of a poly (vinylpyrrolidone-co-vinylpyridine) copolymer having an average molecular weight of 70 K was obtained.

Synthesis Example 5 (Synthesis of Water-Soluble Polymer 5 (Mw = 150K))

 Using the same method as in Synthesis Example 1, except that 0.1 g of dimethyl-2,2'-azobis-2-methylpropionate, an initiator, was used 80.33 g of a poly (vinylpyrrolidone-co-vinylpyridine) copolymer having an average molecular weight of 150K was obtained.

Synthesis Example 6 (Synthesis of Water-Soluble Polymer 6 (Mw = 70K))

  Synthesis Example 1 except that 0.7 g of dimethyl-2,2'-azobis-2-methylpropionate and 127.3 g of vinylimidazole were used as an initiator. 110.5 g of polyvinylimidazole having a weight average molecular weight of 70 K and represented by the following Chemical Formula 4 were obtained using the same method as described above.

[Formula 4]

Synthesis Example 7 (Synthesis of Water-Soluble Polymer 7 (Mw = 70K))

   Synthesis except that 0.7 g of dimethyl-2,2'-azobis-2-methylpropionate, an initiator, and 167.5 g of hydroxyethyl methacrylate were used. Using the same method as in Example 1, 155.85 g of polyhydroxyethyl methacrylate having a weight average molecular weight of 70K and represented by the following formula (5) was obtained.

[Formula 5]

[Examples 1 to 12]

     The water-soluble polymer synthesized in Synthesis Examples 1 to 7 was prepared a resin composition solution for forming a micropattern based on the composition ratios exemplified in Table 1 below.

Example Water soluble polymer 2- (2-aminoethylamino) ethanol 1,1,3,3-tetrakis (methoxymethyl) urea water One 10 g, Synthesis Example 1 1 g - 100 g 2 10 g, Synthesis Example 1 - 1 g 100 g 3 10 g, Synthesis Example 2 1 g - 100 g 4 10 g, Synthesis Example 2 - 1 g 100 g 5 10 g, Synthesis Example 3 1 g - 100 g 6 10 g, Synthesis Example 3 - 1 g 100 g 7 10 g, Synthesis Example 4 1 g - 100 g 8 10 g, Synthesis Example 4 - 1 g 100 g 9 10 g, Synthesis Example 5 1 g - 100 g 10 10 g, Synthesis Example 5 - 1 g 100 g 11 10 g, Synthesis Example 6 1 g - 100 g 12 10 g, Synthesis Example 7 1 g - 100 g

[Comparative Examples 1 and 2]

10 g of water-soluble polymer obtained in Synthesis Example 4 and 100 g of water were used, and the content of 2- (2-aminoethylamino) ethanol was 0.05g and 10g, respectively, as shown in Table 2 below. made.

  Comparative example Water soluble polymer 2- (2-aminoethylamino) ethanol 1,1,3,3-tetrakis (methoxymethyl) urea water One 10 g, Synthesis Example 4 0.05 g - 100 g 2 10 g, Synthesis Example 4 10 g - 100 g

Examples 13 to 24

      Lithography experiments were carried out using the resin composition solutions for forming the micropatterns prepared in Examples 1 to 12, respectively. (These are referred to as Examples 13 to 24.)

First, an organic ARC is coated on a silicon wafer, and a KrF photoresist is coated thereon, followed by exposure and development with an ASML800 (NA 0.93) exposure equipment to obtain a substrate having an L / S pattern of at least 179 nm and at most 183 nm (CD ₀ ). .

Then, the resin composition solution for forming a micropattern made in Examples 1 to 12 was respectively coated on the substrate and dried.

Then, using a developer for one minute soaked in distilled water and then by measuring the FE-SEM (critical dimension) CD, respectively indicated by _A CD. (The CD value prior to the resin coating composition solution for forming a fine pattern referred to as CD ₀₎ shows the measurement results are shown in Table 3.

Sample CD ₀ (nm) CD _A (nm) Example 13 179 175 Example 14 181 174 Example 15 183 164 Example 16 180 160 Example 17 182 154 Example 18 183 150 Example 19 179 140 Example 20 181 141 Example 21 183 137 Example 22 183 136 Example 23 182 155 Example 24 180 152

       As can be seen from the results of Table 2, it was confirmed that the degree of contribution to the refinement of the pattern increases as the molecular weight increases, because the entanglement effect is improved as the molecular weight increases.

In the resin composition of the present invention, for example, as shown in Examples 23 and 24, since there is no unit to generate crosslinking, the gap between the intaglio portion of the micropattern is reduced through a completely different mechanism from the conventional chemical crosslinking mechanism. This is the entanglement caused by physical bonds between the polymer chains in the molecular unit, and as shown in the examples, the change of CD _A value due to the control of the molecular weight of water-soluble polymers of the same composition is not a chemical crosslinking mechanism but a swelling phenomenon of the photoresist resin. It clearly supports the physical mechanism due to the entanglement of water and water-soluble resins.

[Comparative Examples 3-4]

      The micropattern-forming resin composition solution prepared in Example 7 was prepared in the same manner as in Example 19 except that the micropattern-formed resin composition solutions prepared in Comparative Examples 1 and 2 were each coated on the substrate.

Sample CD ₀ (nm) CD _A (nm) Comparative Example 3 180 178 Comparative Example 4 179 -

As can be seen from the results of Table 4, in the case of Comparative Example 3 carried out using the resin composition solution for forming a micropattern made in Comparative Example 1, the effect was insignificant, and the reduction of CD was only 2 nm, and the fine made in Comparative Example 2 In the case of Comparative Example 4 carried out using the resin composition solution for pattern formation, pattern collapse occurred and CD _A measurement was impossible.

      Therefore, when the alkali content is less than 0.1 parts by weight based on 100 parts by weight of water, the effect of the pattern is reduced to a small amount, and when used in excess of 5 parts by weight it was confirmed that the pattern collapse phenomenon occurs.

      Although the embodiment has been described with the L / S pattern, the present invention is not limited thereto and the present invention can be applied to miniaturization of various patterns such as hole patterns.

When the lithography process is performed using the resin composition solution for forming a micropattern according to the present invention, swelling of the photoresist pattern layer is induced by an alcohol or alkali aqueous solution, and the entanglement between the swelled photoresist pattern layer and the water-soluble polymer is performed. And as a result, the interval between the intaglio portions of the photoresist pattern layer can be made fine, so that a fine pattern exceeding the wavelength limit can be formed.

Claims (16)

A resin composition coated on a photoresist pattern layer to form a micropattern, wherein the resin composition includes an aqueous solution containing an alcohol or an alkali and a water-soluble polymer. The resin composition of claim 1, wherein the water-soluble polymer is a homopolymer composed of hydrophilic monomer units or a copolymer between two or more hydrophilic monomer units. The method of claim 1, wherein the water-soluble polymer is at least one hydrophilic monomer unit and vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltri A resin composition for photoresist pattern surface swelling and entanglement formation, characterized in that it is a copolymer comprising at least one monomer unit selected from the group consisting of imidazole and vinyl tetraimidazole. The method of claim 1, wherein the water-soluble polymer is at least one hydrophilic monomer unit and at least one (meth) acryl monomer unit containing a functional group selected from the group consisting of adamantyl group, tricyclodecanyl group, norbornyl group and isobonyl group It is a copolymer which consists of a photoresist pattern surface swelling and the resin composition for entanglement formation characterized by the above-mentioned. The hydrophilic monomer unit of the water-soluble polymer is a hydroxyl group, a carboxylic acid group, an amide group, an amine group, a heterocyclic group, an ether group, an ester group, an acetal group and a sulfonic acid group. 1 or 2 or more functional groups selected from the group consisting of photoresist pattern surface swelling and entanglement-forming resin composition. The hydrophilic monomer unit of the water-soluble polymer is vinyl alcohol, vinyl carbohydrate, acrylic acid, methacrylic acid, ethylene oxide, vinyl hydroxyethyl methacrylate, benzoacrylic acid, vinyl. Pyrrolidone, vinylamine, allylamine, vinylimidazole and vinyloxazoline. The resin composition for photoresist pattern surface swelling and entanglement formation, characterized in that at least one selected from the group consisting of: The vinylpyridine, vinylthiophene, styrene, vinylcarbazole, vinylbenzimidazole, vinylmethylimidazole, vinyldiaminotriimidazole, vinyltriimidazole and vinyltetrade according to the hydrophilic monomer unit number. A resin composition for forming a photoresist pattern surface swelling and entanglement, wherein the ratio of the number of monomer units selected from the group consisting of imidazoles is 0.01 to 0.5. The ratio of the number of (meth) acryl monomer units containing a functional group selected from the group consisting of adamantyl group, tricyclodecanyl group, norbornyl group and isobonyl group to hydrophilic monomer unit number is 0.01 to 0.5. The resin composition for photoresist pattern surface swelling and entanglement formation characterized by the above-mentioned. The method of claim 1, wherein the water-soluble polymer has a weight average molecular weight (Mw) of 5,000 to 1,000,000 photoresist pattern surface swelling and resin composition for forming the entanglement. The method of claim 1, wherein the alcohol is at least one selected from the group consisting of methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, cyclohexanol and hydrobenzoin surface swelling and entanglement formation Resin composition. The resin composition of claim 1, wherein the alkali is an organic amine or an ammonium hydroxide. The method of claim 1, wherein the alkali is 2- (2-aminoethylamino) ethanol, 1,1,3,3-tetrakis (methoxymethyl) urea, ethylenediamine, diethylenetriamine, pyridine, allylamine, A resin composition for forming a photoresist pattern surface swelling and entanglement, characterized in that at least one selected from the group consisting of aminoethanol and triethylamine. The method of claim 1, wherein the resin composition for forming a micropattern comprises 50 to 99% by weight of an aqueous solution containing alcohol or alkali and 1 to 50% by weight of a water-soluble polymer, surface swelling and entanglement formation of the photoresist Resin composition. The resin composition of claim 1, wherein the alcohol or alkali is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of water. a) forming a photoresist resin layer on the substrate; b) exposing and developing the photoresist resin layer to form a photoresist pattern layer; c) coating the photoresist pattern surface swelling and entanglement forming resin composition of claim 1 on the surface of the photoresist pattern layer; d) swelling on the surface of the photoresist pattern layer to form a swollen photoresist pattern layer; e) entanglement between the swollen photoresist pattern layer portion and the water-soluble polymer of the resin composition for swelling the photoresist pattern surface and forming the entanglement; And f) removing the water-soluble polymer portion except for the portion in which the entanglement has occurred, including removing water with an aqueous solution containing water, an alkaline aqueous solution or an organic solvent. A semiconductor integrated circuit device formed by the method of forming a fine pattern of claim 15.

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