TW201038595A - Polymer for forming photoresist pattern and method for forming pattern of semiconductor device using the same - Google Patents

Abstract

A polymer for coating photoresist pattern, which can improve the resolution of a lithography process, and a method for forming pattern for semiconductor device using the same are disclosed. The polymer for coating the photoresist pattern is represented by the following formula. In formula, R* is independently a hydrogen atom or a methyl group (-CH3), R1 is a linear or cyclic hydrocarbyl group of 1 to 18 carbon atoms, R2 is an hydroxyl group (-OH), an carboxyl group (-COOH), or a linear or cyclic hydrocarbyl group of 3 to 10 carbon atoms, 1 to 3 nitrogen atoms and 1 to 3 oxygen atoms, and x and y independently represent mol% of repeating units to total repeating units of the polymer of the formula, and are 5 to 100 mol% and 0 to 95 mol%, respectively.

Description

201038595 VI. Description of the Invention: This application claims priority to Korean Patent Application No. 10-2009-0016965, filed on Feb. 27, 2009. This Korean patent application is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a polymer for coating a photoresist pattern, and more particularly to an polymerization for coating a photoresist pattern and thereby improving the resolution of the lithography process. And a method of forming a pattern of a semiconductor element using the polymer. [Prior Art] As the density of semiconductor elements is increased, a photolithography process is required to form a very small photoresist pattern having a line width of less than or equal to 80 nanometers (nm). In a conventional ◎ photolithography process, a photoresist composition containing a photopolymer and a solvent is coated on a substrate such as a germanium wafer to fabricate an integrated circuit, a solvent in the applied photoresist composition. Then, it is baked and volatilized to form a photoresist layer film. Subsequently, the photopolymer layer exposed to the light pattern of the exposure source is exposed to a change in the photopolymer. For example, visible light, ultraviolet (uv) photoelectron beam, xenon-light, etc. can be used as an exposure source. After exposure, the developer is used to selectively dissolve and - remove the exposed photoresist layer to form a photoresist pattern. Various techniques for improving the resolution of photoresist patterns have been developed in the photolithography process. For example, PCT International Publication No. w〇 2〇〇8/122884 and Ep 4 201038595

1757989 A discloses a method of coating a photoresist pattern by a polymer to reduce the pattern spacing, and riding is shown in the first. Figure 1 shows an embodiment of a conventional method for forming a fine photoresist pattern. As the first! As shown, a conventional method of forming a photoresist pattern includes the steps of forming a photoresist I 120 to a substrate 110 (see A of FIG. 3), and forming a photoresist by exposing and developing the photoresist layer 12 to a desired image. The step of Fig. 122 (see B of Fig. i) and the step of coating the polymer of the micronized material 13 to the photoresist pattern 122 to reduce the line width (see the figure of Fig. Fig. The substrate of the polymer of the micro-material 130 is used to bond the photoresist pattern 122 and the micro-material 30' and then form the boundary layer 132 (see d of the figure) using a solution (such as water) to develop the unreacted portion of the micro-material 13 In order to reduce the interval between the photoresist patterns 122 (see E of FIG. i), a photoresist pattern having a smaller critical dimension (CD) can be formed by the above method. The method of the photoresist pattern reduces the size of the previously formed contact hole (C/H). [Invention] It is therefore an object of the present invention to provide a polymer for coating a photoresist pattern which can be improved. Resolution of the lithography process. Another object of the present invention It is to provide a method of coating a photoresist pattern using the aforementioned polymer to form a high-resolution semiconductor element pattern. A further object of the present invention is to provide a pattern of semiconductor elements by pattern self-alignment, 5 201038595 The method of forming a double pattern with the line-to-line spacing. To achieve the above object, the present invention provides a polymer for coating a photoresist pattern, which is represented by the following Chemical Formula 1: [Chemical Formula 1], R* R * 卜o r2 · 0

I

Ri, . , nh2 In Chemical Formula 1, R* is each a hydrogen atom or a methyl group (_CH3), the rule 1 is a linear or cyclic hydrocarbon group having 1 to 18 carbon atoms, and r2 is a hydroxyl group (_0H), a slow group. (_C00H), or a linear or cyclic hydrocarbon group having 3 to 10 carbon atoms 'i to 3 nitrogen atoms and 1 to 3 oxygen atoms, and each of X and y represents a plurality of polymers represented by Chemical Formula 1. The repeating unit accounts for the molar/〇 of the overall repeating unit and is 5 ii 〇〇 mol % and respectively. Up to 9 ears. The present invention further provides a composition for coating a photoresist pattern, wherein the package 3 is represented by the above Chemical Formula 1, a polymer for coating a photoresist pattern; and a polymer for dissolving a photoresist pattern. Solvent. The present invention also provides a method for forming a pattern of a semiconductor element, comprising the steps of: (1) coating a photoresist as a first photoresist layer onto a substrate, and then exposing and developing the first photoresist layer to form a first a photoresist pattern; (coating a composition containing a polymer for coating a first photoresist pattern and expressing a solvent of the polymer, and then volatilizing the solvent to form a coating layer to (4) applying a coating layer to remove the unreacted coating ... to form an interface layer covering the first photoresist pattern photoresist to fill the interval between the interface layers, In the first-resistance diagram, the first-first-resistance pattern is followed by development to remove the interface layer, so that the first first-resistance pattern and the second photoresist pattern remain on the substrate. The first and second photoresist patterns may be formed between the semiconductor element and the line.

The polymer of the present invention is coated on a first photoresist pattern and subjected to a reaction' followed by development of an unreacted portion of the coating layer derived from the polymer using deionized water to form an interface layer. This will reduce the interval between the first photoresist patterns. Thereby the interface layer 'the second photoresist pattern can be formed between the first photoresist patterns in a self-aligned manner. The double pattern is formed between the lines and lines of the semiconductor pattern. Therefore, the alignment error that may be generated by forming the second photoresist pattern using the exposure apparatus according to the prior art can be reduced. [Embodiment] The present invention and its advantages will be more fully understood from the following detailed description. The polymer previously formed for coating a photoresist pattern according to the present invention is represented by the following Chemical Formula 1, which reacts with the photoresist pattern to form an interface layer surrounding the photoresist pattern. '[Chemical Formula 1] 201038595

Rl,

t, nh2 In Chemical Formula 1, R* is each a hydrogen atom or a fluorenyl group (-CH3), h is a linear or cyclic hydrocarbon group having 1 to 18 carbon atoms, and R2 is a hydroxyl group (-OH) or a carboxyl group (- COOH), or a linear or cyclic hydrocarbon group having from 1 to 3 nitrogen atoms and from 1 to 3 oxygen atoms of 3 to 10 carbon atoms. R] may be a linear or cyclic compound or an aryl group, and may contain a hetero atom such as an oxygen atom (0), a nitrogen atom (N), a sulfur atom (S), or the like as the case requires. Detailed examples of R, include -CH2—, 'CH2CH2*~~, —CH2CH2CH2—, """CHaCHaCHzCHa*~, -CH2CH2CH2CH2CH2~~·, •CH2CH2CH2CH2CH2CH;r-CHCH2—CH3, -CHCH2—o» chch2-CH3 CH3 -CHCH2CH2—ch3 -ch2ch2-〇-ch2ch2-ch3 —ch2cch2— , ch3 CH2CH;t〇—CH2CH2-〇-CH2CHr ch2oh ch3 -CH2CCH2CH2 ch3 ch2cch2-ch2oh —CHCH2-0-CHCH2-O-CHCH2— Ch3 I ch3 ch3

CH2-* —CH2·

'corpse 、,, -ο-s-ο-, etc. R2 is preferably a heterocyclic group such as an imidazolyl group or an indolylamine group, more preferably a pyrrolidone group. In Chemical Formula 1, x and y each represent a molar unit of the repeating unit in the polymer of Chemical Formula 1 as a percentage of the total repeating unit, and X is 5 to 100%.

Acid-diffusing-baking causes the acetal to be deprotected, thereby reducing the solvent selectivity of the polymer. If the y content is too large, it will lower the adhesion between the polymer and the resist pattern. A detailed example of the polymer for coating a photoresist pattern according to the present invention is represented by the following Chemical Formula 2a-2g. In Chemical Formula 2a-2g, X and y have the same definitions as Chemical Formula 1. [Chemical Formula 2a]

〇 [Chemical Formula 2b]

[Chemical Formula 2c] 201038595

[Chemical Formula 2e]

OH Ο

Ο

'ΝΗ2 [Chemical Formula 2f] . [Chemical Formula 2g] 聚合物 The polymer for coating a photoresist pattern of the present invention can be synthesized by using a known initiator (for example, an octagonal diisobutylene method) - To manufacture 'the ethylene monomer includes one L. —/ 1 , R_*, β竣. ^ Κ·2, etc. In the polymer of Benming Ming, the content of each repeat unit is proportional to the amount of monomer used. The polymer for coating the silk pattern may be agglomerated or a scrambled copolymer. The weight average molecular weight (Mw) of the polymer of the present invention is preferably 201038595.

Ο 5,000 to 100,000, more preferably 5 〇〇〇 to 2 〇, 〇〇 (). The polymerity distribution (p〇lydiSpersity, PD) of the polymer of the present invention is preferably from 1.0 to 5.0', more preferably from 1.0 to 2.0. If the weight average molecular weight of the polymer and the degree of polymerization of the polymer exceed the above range, the properties of the coating layer for coating the photoresist pattern are weakened. Since the polymer molecule of the present invention has an amine group, the photoresist pattern is easily adhered to the polymer for coating the layer of the present invention, and the coating does not damage the photoresist pattern. The polymer for coating a photoresist pattern of the present invention can be deprotected by the acid generated by exposure and baking. Moreover, since the deprotection of the acetal group in the polymer molecule and the contrast of the development step are improved, the adhesion between the first photoresist pattern and the polymer is lowered, and the development and migration can be easily performed using deionized water or the like. In addition to the polymer of the present invention for coating a photoresist pattern. The polymer for coating a photoresist pattern of the present invention can be used as a composition dissolved in a solvent. The solvent for coating the composition of the photoresist pattern may be water, preferably deionized water. If necessary, a mixed solvent of water and alcohol can also be used. In the composition for coating the photoresist pattern, the content of the polymer of the formula is 0.5 to 30% by weight, preferably 3 to 1% by weight, and the balance is a solvent. If the polymer content is too small, the polymer layer after the formation of the coating layer is too thin to form a coating layer of a predetermined thickness; if the polymer content is too large, the uniformity of the coating layer is lowered. In the composition for coating a photoresist pattern of the present invention, examples of the alcohol which can be used in combination with water include lower alcohols having 1 to 4 carbon atoms, such as methanol and ethanol, and the alcohol component accounts for 〇 to 5 总体 of the total composition. The weight %, preferably from 1 to 50 by weight, more preferably from 5 to 25% by weight. If the content of the alcohol component is too small, 1 11 201038595 will lower the uniformity of the coating layer; if the content of the alcohol component is too large, the first photoresist pattern may be dissolved, so that the second photoresist pattern cannot be formed. Furthermore, if necessary, the composition for coating a photoresist pattern of the present invention may further comprise a conventional photo acid generator (PAG), a thermal acid generator (TAG), or an organic The base is used as a quencher, a surfactant, and the like. The pag generates an acid component upon irradiation and de-protects the protecting group of the polymer used to coat the photoresist pattern. Any compound that produces an acid component when exposed to light can be used as a PAG. Preferably, an onium salt compound (e.g., an organic sulfonic acid), a phosphonium salt compound (e.g., a phosphonium salt) or a mixture thereof can be used. Non-limiting examples of PAG include phthalimidotrifluoro methane sulfonate, dinitrobenzyl tosylate, n-decyl disulfone, Naphthylimido trifluorome thane sulfonate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, hexafluoride Diphenyl iodonium hexafluoroantimonate, diphenyl p-methoxyphenyl sulfonium triflate, triphenylsulfonium hexafluoroantimonate , triphenylsulfonium triflate, dibutylnaphtylsulfonium triflate, and mixtures thereof. If PAG or TAG is used, it is preferably used in an amount of from 0 to 20 parts by weight, more preferably from 0.05 to 20 parts by weight, based on the weight of the polymer 100 parts by weight of 201038595. It is preferably from 0.1 to 10 parts by weight. The amount of S PAG or TAG is too high. The photo-sensitivity of the t-form is reduced, resulting in insufficient deprotection of the protecting group. If the amount of PAG or TAG is too large, the target pAG or TAG generates an excess of acid' so that the coating layer The shape is not good. The surfactant which can be used in the present invention is preferably a water-soluble surfactant, but an anionic surfactant, a cationic surfactant and an amphoteric surfactant can also be used. 〇 For example, an alkylbenzenesulfonate, a higher halogenated amine, a quaternary ammonium salt, a snap salt, an amino acid, a brewed imine, a continuous amine surfactant, or a mixture thereof may be used. The content of the surfactant is based on the weight of the entire composition for coating the photoresist pattern, and the weight of the 里1 to 2 is preferably 〇. If the surfactant content is too small, the uniformity of coating will be reduced; if the surfactant content is too large, the film layer will be lost in a large amount during the process of removing the coating layer by water, and it cannot be effectively formed on the first pattern. Coating layer. Next, please refer to Fig. 2, which illustrates a method for forming a pattern of a semiconductor element. The first photoresist layer 20 is formed on a substrate 1 (e.g., a wafer, aluminum, etc.) (see A of Fig. 2). The first photoresist layer 20 is exposed and developed with the desired image to form a first photoresist pattern 22 (see B of Fig. 2). The composition for coating the first photoresist pattern 22 is coated, followed by volatilization of the solvent in the composition to form a coating layer 3 (see C of Fig. 2). The polymer of the first photoresist pattern 22 and the coating layer 30 is adhered by a method such as baking the coating layer 30, or the acid is diffused from the first photoresist pattern to the polymer of the coating layer 30 so as to be covered by the coating. Interface formed by the material 201038595 Layer 32 is developed around the first photoresist pattern 22 (see Figure 2 for developer (such as water, alcohol, aqueous alkaline solution, and mixtures thereof) and removes unreacted coating layer 30 parts, in order to reduce the gap between the first light barrier

The spacer (open area) (see Ε of Fig. 2) is coated with a second photoresist to fill the space between the interface layers 32 to form a second photoresist pattern 42 (see F of Fig. 2). If necessary, the acid is diffused to the second photoresist pattern 42 by exposing or baking the second photoresist pattern 々a to enhance the hardness of the second photoresist pattern 42. In this case, the second photoresist is preferably a photosensitive photoresist which can change properties under light irradiation. Next, using an alkaline compound (such as sodium hydroxide, potassium hydroxide, sodium carbonate, and methyl hydrazide (10%), which has been dissolved in 〇1 to 1% by weight of an alkaline compound, is removed by development. The interface layer 32, and the first photoresist pattern U and the second photoresist pattern 42 remain on the substrate (see G of FIG. 2). Thus, a photoresist pattern having a smaller spacer width than the prior art will be formed. The solubility of the developing solution due to the first-resist pattern 22, the second photoresist pattern 42, the coating layer 3, and the interface layer 32 becomes different depending on the material properties, baking or exposure. 'Control development conditions or development time The interface layer 32 can be selectively developed. Especially in the polymer example for coating a photoresist pattern of the present invention, the 'acid diffusion process is performed by exposing or baking after forming the second photoresist pattern 42. The properties of the polymer of the interface & 32, the first photoresist pattern 22 and the photoresist pattern of the two photoresist patterns 42 may be changed more differently. This is because the acid diffusion process will be deprotected for coating light. _ the polymer of the case. 22 and the second photoresist pattern 42 are used as a mask and the substrate 1 () is treated by the method of (4), or the property of the open region of the substrate 201038595 is changed to form a semiconductor element pattern. Or a vaporized germanium (KrF) photoresist can be used as a photoresist for forming the germanium-resist pattern 22 and the second photoresist pattern 42. For example, by forming a linear second photoresist pattern 42 to the first photoresist The interval between the patterns U can form a high-resolution map close to 30 nanometers (nm), "in the method for forming a pattern of a semiconductor element, the polymer used for coating the layer 3 of the interface layer 32 The space for forming the second photoresist pattern Q 42 is reserved for the cover material, thereby forming a double photoresist pattern. The preferred embodiment will be described in more detail below to more clearly illustrate the present invention. However, the present invention is not limited to the following examples. [Example 1-1] Preparation of a polymer represented by Chemical Formula 2a 11.1 g ((M mole) of 1-vinylpyrrolidone (1-vinyl-Pyrro Ud〇ne), 13.2 g (0.1 mol) of acrylic acid Acrylic acid aminomethoxymethyl ester and 偶7 g of even double Isobutyronitrile (AIBN) was added to the 0 reactor and dissolved in 100 g of acetonitrile. Then, the gas was removed by ampoules using a freezing method, and the degassed reactant was at 70. (: Polymerization for 24 hours) After the completion of the polymerization, the reactant was gradually added to the excess of the diethyl bond to precipitate the product, and then the product was dissolved in acetonitrile. The dissolved product was reprecipitated in diethyl ether to prepare a polymer represented by the chemical formula 2a. The weight average molecular weight (Mw), number average molecular weight (?n) and degree of polymerization (PD) of the material were measured by Gel Permeation Chromatography (G1) C) (GPC analysis: Mn = 29,000; Mw = 81,000; PD = 2.79). 15 201038595 [Example 1-2] Preparation of a polymer represented by Chemical Formula 2b ^ In addition to using 14.5 g (0.1 mol) of acrylic acid aminoethoxymethyl ester in place of 13.2 g (〇·1 mol) A polymer represented by Chemical Formula 2b was prepared in the same manner as in Example 1-1 except for the methoxy methoxy acrylate. The weight average molecular weight (Mw), number average molecular weight (??) and degree of polymerization (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 26,500; Mw = 69,800; PD = 2.63). [Example 1-3] Preparation of the polymer represented by Chemical Formula 2c except that 19.9 g (0.1 mol) of 'amino-cyclohexyloxymethyl ester' was used instead of 13.2 g (〇·1 mol) The polymer represented by Chemical Formula 2c was prepared in the same manner as in Example 1-1 except for the amino-f-oxymethyl acrylate. The weight average molecular weight (Mw), number average molecular weight (??) and degree of polymerization (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 24,800; Mw = 78,500; 〇 PD = 3.17). [Example 1-4] Preparation of a polymer represented by Chemical Formula 2d In place of 13.2 g (0.1 mol) of aminoguanidine acrylate, except for 4-amino-phenoxymethyl ester of 〇·1 mole was used. A polymer represented by Chemical Formula 2d was prepared in the same manner as in Example 1-1 except for the oxymethyl ester. The weight average molecular weight (Mw), number average molecular weight (?n), and degree of polymerization distribution (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 26,900; Mw = 77,000; PD = 2.86). [Example 1-5] Preparation of Polymer 16 represented by Chemical Formula 2e 201038595 In addition to the use of 8.6 g (0.1 mol) of vinyl acetate (1 vinyi acetate) in place of 1 M g ((M mole) of fluorenylpyrrolidone, The polymer represented by Chemical Formula 2e was prepared in the same manner as the Example. The weight average molecular weight (Mw), number average molecular weight (_ and degree of polymerization distribution (PD) of the obtained polymer were measured by GPC (GPC analysis: Mn = 19 〇〇) Oh ;

Mw = 68,400; PD = 3.60) 〇 [Example 1-6] Preparation of polymer 表示 represented by chemical formula In addition to using 13.9 g (0.1 mol) of 1-vinyl caprolactame A polymer represented by Chemical Formula 2f was prepared in the same manner as in Example 1-1 except for gram (0.1 mol) of oxime-vinylpyrrolidone. The weight average molecular weight (Mw), number average molecular weight (?n), and degree of polymerization distribution (PD) of the obtained polymer were measured by gpC (Gpc analysis: • Mn = 30,200; Mw = 75,600; PD = 2.50) ° [Example 1 7] Preparation of polymer represented by Chemical Formula 2g Formula 2g was prepared in the same manner as in the example dip except that 7'2 g (0.1 mol) of acrylic acid was used instead of 11_1 g (0.1 mol) of 1-vinylpyrroleium. Represents the polymer. The weight average molecular weight (Mw), number average molecular weight (Mn) and degree of polymerization distribution (pD) of the obtained polymer were measured by GPC analysis. Mn = 29,500; Mw = 78,600; PD = 2.66. [Examples 2-1 to 2-8] Preparation of a composition for coating a photoresist pattern As shown in Table 1 below, 2.7 g of a polymer for coating a photoresist pattern (which is respectively according to Example 1-1 to 丨) 7 (chemical formula 2a to 2g)), 3 grams of water-soluble surfactant (sulfonamide surfactant), tci limited ~ 〇. 1 gram of TAG (two gas A acid 录 record (amm〇nium 17 201038595 trifluoromethane sulfonate, Aldrich Co., Ltd.)) and 〇15 grams of PAG (triPhenylsulfonium triflate) dissolved in 17.0 grams of deionized water, or dissolved in deionized water Isopropanol was filtered in a solvent mixed at a ratio of 6:4 and filtered through a 2 micrometer (Pm) disk filter to prepare a composition for coating a photoresist pattern. Table 1 Polymer polymer content interface Active agent TAG PAG Deionized water alcohol Example 2-1 Chemical formula 2a 2.7 g 0.3 g 0.1 g - 17 g Example 2-2 Chemical formula 2b 2_7 g 0.3 g 0.1 g - 17 g - Example 2-3 Chemical formula 2c 2.7 g 0.3 g 0.1克 - 17g - Example 2-4 Chemical Formula 2d 2.7g 0.3g 0.1g - 17g - Example 2-5 Chemical Formula 2e 2·7g 0.3g 0 .1 g - gram - Example 2-6 Chemical formula 2f 2.7 g 0.3 g 0.1 g - 17 g - Example 2-7 Chemical formula 2g 2.7 g 0.3 g 0.1 g - 17 g - Example 2-8 Chemical formula 2g 2.7 g 0.3 g 0.1克 0.15 g 10.2 g 6.8 g [Examples 3-1 to 3-8] to form a Q semiconductor element pattern for coating the composition of the photoresist pattern 2 g of an ArF photoresist polymer represented by the following Chemical Formula 3 (molecular weight (Mw) : 10,100 ; degree of polymerization distribution (PD): 1·89 ; a : b : c (mol %) = 45 : 40 : 15), 0.02 g of triphenylsulfate trifluorosulfate and 〇. 1 g of triethanolamine is dissolved in 10 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 〇.2μηι filter to prepare a first photoresist pattern. Composition. [Chemical Formula 3] 18 201038595

OH The above photoresist composition was used to form a 50 nm pattern (first photoresist pattern) having a line width to space ratio of 1:3. The photoresist composition prepared according to Examples 2-1 to 2-8 was spin-coated on top of the wafer on which the first photoresist pattern was formed to form a thin layer, followed by 1 50° in an oven or on a hot plate. C soft bake has been applied to the wafer for 60 seconds. The baked wafer was immersed in a 2.38 wt% aqueous solution of tetradecyl ammonium arsenate (TMAH) or deionized water for 60 seconds to develop to cover the first photoresist pattern (forming the interface layer). The line width variation of the coating pattern formed by the above method is shown in Table 2. Table 2 Line width of the first photoresist pattern; critical dimension (CD) Line width after coating the first photoresist pattern with the interface layer Example 3-1 50 nm 82 nm Example 3-2 50 nm 78 nm Example 3-3 50 nm 78 nm Example 3-4 50 run 65 nm Example 3-5 50 nm 86 nm Example 3-6 50 nm 85 nm Example 3-7 50 run 76 nm Example 3-8 50 nm 82 nm

Next, 2 g of a KrF photoresist polymer represented by the following Chemical Formula 4 (molecular weight (Mw): 14,800; degree of polymerization distribution (PD): 2.02; a: b (mole ° /.) = 65 : 35) And 0.01 g of triethanolamine was dissolved in 10 g of C19 201038595 diol monoterpene ether acetate (PGMEA) and filtered through a filter of 〇.2 μηη to prepare a composition for coating a photoresist pattern. [Chemical Formula 4]

0, a second photoresist pattern is formed at intervals between the first photoresist patterns, and a photoresist composition (resist for the second pattern) is spin-coated on the wafer, and in an oven or on a heating plate, Soft-bake at 12 rc for 6 sec. The immersed wafer was immersed in a 3.8 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds to remove the coated portion (interface layer). The second photoresist pattern having a lower height than the first photoresist pattern thus forms an interval between the first photoresist patterns. Fig. 3 is a scanning electron micrograph of the photoresist pattern formed by the composition of Example 3-5. As shown in FIG. 3, the first photoresist pattern having a line width and an interval of 1: 3 can be easily formed between the first photoresist patterns by using the self_align_double-patterning process of the present invention. Therefore, when the second resistive pattern is formed by using the polymer for coating a photoresist pattern of the present invention, an exposure apparatus using a light source such as a head 〇i93 nm, 248 nm does not need a mask alignment process, and the self Aligning the double patterning process requires baking and exposing the wafer to perform 0. BRIEF DESCRIPTION OF THE DRAWINGS 20 201038595 Fig. 1 is a schematic view of a conventional method for forming a fine photoresist pattern. Fig. 2 is a schematic view showing an embodiment of a method for forming a pattern of a semiconductor element according to the present invention. Fig. 3 is a scanning electron micrograph of the photoresist pattern formed by the composition of Examples 3-5. [Main element symbol description] 〇10 Substrate 20 Photoresist layer 22 First photoresist pattern 42 Second Photoresist pattern 30 coating layer 32 interface layer 110 substrate 120 photoresist layer 122 photoresist pattern 130 micro-material 132 boundary layer 21

Claims (1)

201038595 VII. Patent application scope: l A polymer for coating a photoresist pattern, which is represented by the following chemical formula 1: [Chemical Formula 1] , nh2 〇 in the formula 1, R* is a single hydrogen atom or a monomethyl group (-CH3), Rj is a straight chain or cyclic hydrocarbon group having 1 to 18 carbon atoms, and 1 is a hydroxyl group (-OH) a mono-carboxy group (-COOH), or a straight-chain or cyclic hydrocarbon group having 3 to 1 carbon atoms, 3 to 3 nitrogen atoms and 1 to 3 oxygen atoms, and χ and y each represent the chemical formula 1 The plurality of repeating units of the polymer are expressed as % of the total repeating unit, and are 5 to 1 mole % and 0 to 95 mole %, respectively. D 2. The polymer for coating a photoresist pattern according to claim 1, wherein Ri is a straight chain or a cyclic alkyl group or a straight chain or a cyclic aryl group, and R 2 is a heterocyclic group. . 3. The polymer for coating a photoresist pattern according to claim 1, wherein 1 ^ is selected from the group consisting of _CH2 -, -CH2CH2~, -CH2Ch2CH2~, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, _CH2CH2CH2CH2CH2CH2 —CH2CH2-〇-CH2CH2—,CH2CH2-O-CH2CH2-0-CH2CH2—, ch^,?||CH2CH2—- 22 201038595 CH3 —CH2〇CH2 ch3 ch3 —CH2CCH2CH2- ch3 ch2oh —ch2cch2— ch2oh —CHCH2 -0-CHCH2- ch3 ch3 ch2- cx^o IH,f, -CHCH2-O-CHCH2-0-CHCH2 ch3 ch3 ch3 Ο And CH2 and a group consisting of an imidazolyl group or an intrinsic amine group, and r2 4. The polymer for coating a photoresist pattern according to claim 1, wherein the polymer The weight average molecular weight (Mw) is from 5,000 to 100,000, and X is from 10 to 90 mol%, and y is from 10 to 90 mol%. 5. The coating for coating a photoresist pattern as described in claim 1 of the patent application. 23 201038595 (Chemical Formula 2d) 9 OH (chemical formula 2e) A group consisting of NH2 (chemical formula 2f) and NHa (chemical formula 2g), and in the chemical formula 2a-2g, the definitions of 'x, y' are the same as those of the chemical formula 1. 〇6. A composition for coating a photoresist pattern, comprising: a polymer 'represented by the following chemical formula 1 and used for coating a photoresist pattern; and a solvent 'for dissolving for coating the a photoresist pattern of the polymer; [Chemical Formula 1] , nh2 In Chemical Formula 1, R* is each a hydrogen atom or a methyl group (-ch3), and R1 is a linear or cyclic hydrocarbon group having 1 to 18 carbon atoms, and the core is a hydroxyl group (-〇H). A slow-chain (-CO〇H), or a straight-chain or cyclic hydrocarbon group having 3 to 10 carbon atoms, 丨 to 3 nitrogen atoms and 1 i 3 oxygen atoms, and X and y each have no chemical formula! The plurality of repeating units of the polymer represented represent % of the moles of the repeating unit, and are 5 to 10% by mole and 0 to 95% by mole, respectively. 24 201038595 7. The sixth aspect of the patent application, wherein the solvent is the group of deionized water for coating a photoresist pattern as described in the item. 8. The composition for coating a photoresist pattern as disclosed in the paragraph 1 of the patent application, wherein the solvent is a mixture of leeches and water, and the content of the alcohol accounts for the overall composition. 1 to 5 wt% of the substance. The composition for coating a photoresist pattern according to claim 6, further comprising a photoacid generator or a heat which is 0.05 to 20 parts by weight based on the weight of the polymer (10). Acid generator. 10. The composition for coating a photoresist pattern according to claim 6 of the patent scope, further comprising a surfactant selected from the group consisting of alkylbenzene sulfonates, advanced functional amines, and fourth-order a group consisting of a salt, a burnt bite salt, an amino acid, a quinone imine, and a sulfonamide surfactant, wherein the surfactant content is 100 parts by weight of the total composition. It accounts for 0.01 to 2 parts by weight. 11. A method for forming a pattern of a semiconductor device, comprising the steps of: applying a first photoresist to a substrate to form a first photoresist layer, and exposing and developing the first photoresist layer to form a plurality of first photoresist patterns; a coating for coating a composition of the first photoresist pattern, comprising a polymerization 25 201038595 for coating the first photoresist pattern and represented by the following Chemical Formula 1, And dissolving a solvent of the polymer, and then volatilizing the solvent to form a coating layer onto the first photoresist patterns; [Chemical Formula 1] / .R*. R* ο I Ri, nh2 in the chemical formula In 1 , R* is individually a hydrogen atom or a monomethyl group (CH3), l a straight chain or cyclic hydrocarbon group having 1 to 18 carbon atoms, which is converted into a monohydroxy group (-OH), a fluorenyl group (_c〇〇H), or has 3 to 1 carbon atoms, and has 3 nitrogen atoms. A straight-line or cyclic hydrocarbon group of an atom and U 3 oxygen atoms, and χ and y each represent the chemical formula! The plurality of repeating units of the polymer are represented by the molar % of the total repeating unit, and are respectively 5 to 1 〇〇 mol % and 0 to 95 mol %; the coating layer and the _th photoresist Patterning, then removing the unreacted portion of the coating layer by development to form a plurality of interface layers covering the first photoresist patterns; applying a second photoresist to fill a space between the interface layers to Forming a plurality of second photoresist patterns; and developing and removing the interface layers, the portions of the first photoresist patterns causing the first photoresist patterns and the second photoresist patterns to remain on the substrate . 1 . The method for forming a semiconductor device pattern described in claim 11 wherein the unreacted portion of the coating layer is removed by using a ruler to remove the interface layers. Weight% of 26 201038595 An experimental aqueous solution. 13. The method for forming a pattern of a semiconductor device according to claim 11, further comprising the steps of: exposing or baking the second photoresist patterns to increase the hardness of the second photoresist patterns. . 27