TW200921281A - Polymer for forming organic anti-reflective coating layer and composition including the same - Google Patents

Abstract

A polymer for forming an organic anti-reflective coating layer which has superior adhesiveness to a substrate and high refractive index, and a composition including the same are disclosed. The polymer for forming an organic anti-reflective coating layer includes a repeating unit represented by following Formula, wherein, R1 is a hydrogen atom or a methyl group (-CH3), R2 is S, O or NH, and R4 is a group having a hydroxy group (-OH).

Description

200921281 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a polymer for forming an organic anti-reflective coating, in particular, the present invention relates to a polymer and a composition comprising the same Used to form an organic anti-reflective coating having excellent adhesion to a substrate and having a high refractive index. [Prior Art] In general, in a photolithography process, a light source that emits short-wavelength light (for example, an A r F excitation laser of 193 nm) is conventionally used to improve the resolution of a photoresist pattern. . However, as the exposure wavelength becomes shorter, the interference caused by the light reflected from the etching layer of a semiconductor substrate during illumination increases. This optical interference phenomenon includes undercuts and/or notches on a photoresist pattern that can destroy the uniformity of the shape of the photoresist pattern and the thickness of the pattern. To overcome this problem, a bottom anti-reflective coating is conventionally applied between the etch layer and the photoresist layer to absorb the illuminating light. This anti-reflective coating absorbs the illuminating light and prevents the resist pattern from collapsing due to reflected light. According to the material used to form the organic anti-reflective coating, the organic anti-reflective coating can be divided into an inorganic anti-reflective coating formed of titanium, titanium dioxide, titanium carbide, chromium oxide, carbon, amorphous stone, and the like. And an organic anti-reflective coating formed from a polymer. Compared to inorganic anti-reflective coatings, organic anti-reflective coatings generally do not require complex and expensive methods for forming such anti-reflective coatings, such as vacuum deposition equipment, chemical vacuum deposition apparatus, sputtering apparatus, and the like. The device has strong absorption of radioactive light at the same time, and is insoluble in the current process during the photoresist drying process (for example, the anti-anti-step, [the invention is due to the layer of the coating of the poly-excited layer) The group of polymers is a repeating poly-polymer which has better adhesion to the substrate and a high refractive index. These anti-reflective coatings are achieved in the early days: in the agent. In addition, it is not in the photoresist. Coating, heating, and drying of the layer 'a small amount of material diffuses from the organic anti-reflective coating to the photoresist layer' and the organic anti-reflective coating has a superior surrender rate in the dry etching layer of the photolithography process. However, in the photolithographic etching process using the various types of light sources ArF to excite lasers, the characteristics of conventional conjugates for forming luminescent coatings have not been satisfactory, for example, to the opposite substrate. Adhesion 'light refractive index and so on. Content;] Therefore, one of the objects of the present invention is to provide an organic anti-reflection

Another object of the invention is to provide an organic anti-reflective coating that reduces or prevents the occurrence of notches or undercuts in photolithographic etching processes using various types of light sources (e.g., ArF(R)). 2 OBJECTIVE - To provide an organic antireflective coating which can be prepared at a very low cost and which comprises the polymer. And other objects, the present invention provides a polymer comprising - by the following formula i Formula 1] in the form of a formula 200921281 wherein 1 is a hydrogen atom or a methyl group (-CH3), and R2 is S, 0 or NH and R4 is a group having a hydroxyl group (-OH). The present invention also provides a composition for forming an organic anti-reflective coating comprising: 0.1 to 69.9% by weight of a polymer having a repeating unit of formula 1 0.1 to 30% by weight of a light absorbing agent for receiving an illuminating light; and 30 to 99.8% by weight of an organic solvent for dissolving the polymer. The organic anti-reflective coating and composition made of the polymer have excellent adhesion to a base and a high refractive index. This organic anti-reflective coating minimizes or prevents notches or undercuts in the photolithographic etching process and increases the engraving rate. [Embodiment] Advantages and inventions of the present invention will become more apparent from the following detailed description. A polymer package for forming an organic anti-reflective coating according to the present invention is a repeating unit represented by Formula 1, [Formula 1]

Wherein Ri is a hydrogen atom or a methyl group (_CH3), R2 is S, hydrazine or NH, 200921281 and FU is a group having a hydroxyl group (-〇H), preferably a CrC^oC having a hydroxyl group (-OH) That is, a carbon number is between 1 and 20) a hydrocarbon group, and an unnecessary one contains a hetero atom such as sulfur. A preferred R4 example includes

Wait. In the polymer according to the present invention, the molar % of the repeating unit of Formula 1 is from 1 to 99 mol%, preferably from 1 to 98 mol%, more preferably than the total repeating unit constituting the polymer. It is 5 to 90% by mole. The other repeating units of the polymer may be any other type of repeating unit used to make polymers of conventional organic anti-reflective coatings. As shown in the formula la, preferred polymers for forming an organic anti-reflective coating according to the present invention further comprise repeating units having R3 and/or Rs. [式la]

In formula la, each R is hydrogen or methyl (-CH3); each R2 is S, 0 or NH ', respectively, and R3 is a hetero atom containing sulfur 'preferably C3 containing sulfur a heterocyclic group of C1(), and more preferably a C3~C10 heterocyclic group containing sulfur and nitrogen; R4 is a group having a hydroxyl group (-OH), preferably having a hydroxyl group (-OH) 200921281 Wide (the hydrocarbon group of ^ is trapped, and it is not necessary early and Ra) has 3 such as sulfur, the pyrogen 5疋 has a stupid group, and preferably a 疋/, a hundred-base c Γ hydrocarbon Base, n A _ A 20 group, and non-essential may contain heteroatoms such as sulfur; and a, b and c represent moles of 113⁄4 different revising units compared to the total repeating unit constituting the polymer And respectively, are 98% of Mo, % of 1 to 98%, and 〖~98% of Mo, and preferably are 5~9〇%, 5~卯夭/. and 5~9〇

<〇H

Ff 0/ D ear / 〇. Preferred examples of R4 include,

The following formula can be used to produce the polymer of Formula 1a. For example, (〇 let a heterocyclic compound including sulfur (S) react with (meth)acrylic acid or (meth)acrylic acid dentate to produce an unsaturated vinyl monomer having R2 and R3, (η) let A compound having a hydroxyl group (-OH) is reacted with (meth)acrylic acid or a (meth)acrylic acid halide to produce an unsaturated vinyl monomer having R·2 and R4, and (iii) a compound having a phenyl group (mercapto)propanol acid or (hydrazino) acrylate reaction 'to produce an unsaturated ethylene monomer having B.2 and Rs, and reacting the product of reaction (ii) with reaction (i) and/or The product of lH) is polymerized to produce a polymer of formula la.

Examples of SH heterocyclic compounds including sulfur (s) include ^/S (formula 2a), 9 200921281

OH

HO

NH =〇 S HI person (Formula 2b), \=/ (Formula 2c), (Formula 2d),

SH N person S (style 2e), SH

OH h2n SH person (formula 2f), \=7S (formula 2g), C/(formula 2h), VjS (formula 2i), 0H (formula SH N human S 2j), h 2 7 (formula 2k), etc. . HO HO (

Examples of the R4 compound having a hydroxyl group (-OH) include OH (formula 3a), oh (formula 3b), and the like.

HO

Examples of OH compounds having a phenyl fluorene include / (Formula 4a)

S (formula 4b) and so on.

OH

OH

‘0 (Formula 4 c), (Formula (Equation 4 e) 10 200921281) (i) Examples of heterocyclic compounds including sulfur-containing unsaturated ethylene monomers

=Q =0 =±〇 Q. Includes W/ (Formula 5 a), (Formula 5 b)

S

HN _m φ Q. (formula 5e), sh (formula 5f), \=/ (formula 5§), ^/ (formula 511) human Φ Λ (formula 5i), π (formula 5j), (formula 5k), The actual example of the unsaturated vinyl monomer compound having the hydroxyl group (-OH) of (ii) includes a lake: (Formula 6a) 0y£y%in

Examples of the unsaturated vinyl monomer compound having a phenyl group of the formula (iii) include: 200921281

The polymer used to form the organic anti-reflective coating layer according to the present invention can be produced by a conventional polymerization method such as radical polymerization, solution polymerization, bulk polymerization, and the like. For example, the free radical polymerization in solution can be carried out in the following manner: (i) dissolving each monomer in a polymerization solvent, adding a polymerization initiator thereto, and (iii) under an inert atmosphere ( For example, nitrogen or argon) performs a polymerization reaction. A conventional polymerization solvent can be used as the solvent for polymerization of the present invention, and examples of the solvent include cyclohexanone, cyclopentanone, tetrahydrofuran (THF), dimethylformamide, diterpene, and sb. Dioxane), acetophenone, benzene, toluene, dinonylbenzene, mixtures thereof, and the like. A conventional polymerization initiator can be used as the polymerization initiator of the present invention, and examples of the polymerization initiator include phenylhydrazine peroxide, 2,2'-azobisisobutyronitrile (AIBN), and B.醯Peroxide, Laurel 12 200921281 Peroxide, tert-butyl peracetate, -j-gan, ^ & butyl butyl peracetate hydrogen, di-tert-butyl peroxide and mixtures thereof, and the like. The obtained polymer can be purified by crystallization by a crystallization method, and the crystallization solvent includes a low carbon number alcohol, each of them, a compound compound, water, and a mixture thereof, such as diethyl ether, petroleum ether, methanol, Isopropyl alcohol and so on. According to the present invention, the weight average molecular weight (Mw) of the polymer used to form the organic anti-reflective coating is preferably 丨〇〇〇 to 丨〇〇, 〇〇〇, preferably 疋 5, 〇〇〇 Up to 50,000 rooms. If the molecular weight is less than ι, 〇〇〇, the organic anti-reflective coating can be dissolved by a photoresist. If the molecular weight exceeds 1 Torr, hydrazine may reduce the solubility of the polymer in the solvent and may increase the etching rate of the organic anti-reflective coating during the dry etching process. Since the polymer of formula la includes a warp group, a network structure can be formed via a thermal crosslinking reaction. The formula jat 5 property 彳·*·疋 includes a heterocyclic group having sulfur (and optionally nitrogen) and thus has a high refractive index at 193 nm "because the polymer has a relatively low refractive index" The thickness of the organic anti-reflective coating. Further, the polymer represented by the formula la includes a phenyl group. Therefore, the organic anti-reflective coating made of this polymer has a relatively reliable light absorption at 193 nrn. * The composition for forming an organic anti-reflective coating according to the present invention includes (i) including the repeating unit of Formula 1. a polymer, (ii) a light absorber, and (丨丨i) a solvent. The amount of the polymer used in the composition may vary depending on the molecular weight of the polymer 'the thickness of the organic anti-reflective coating, etc.' and is polymerized compared to the total amount of the composition used to form the organic anti-reflective coating 200921281. The amount of the substance is preferably from 1 to 6 9.9 wt%, more preferably from 1 to 48 wt%. If the amount of the polymer is less than 0.1% by weight or more than 6.99% by weight, the organic anti-reflective coating may not be formed or the physical properties of the resulting organic anti-reflective coating (eg, film uniformity) may not be ideal. In order to improve the coating uniformity of the composition and to improve the viscosity and cohesion of the coating (c 〇 h e s i ο η), the composition of the present invention may comprise a conventional polymer and or an additive such as a crosslinking agent. Examples of conventional polymers include: polymers and/or from acrylates, hydrazine acrylates, styrenes, hydroxystyrenes, oxyalkylenes, oxindoles, decylamines, imines, esters, ethers, vinyl acetate a copolymer of an ester, a vinyl ether sulfhydryl group, a vinyl ether-cis-butadiene anhydride, and a urethane; a phenol resin; an epoxy resin; a varnish resin; a mixture of a polymer and a resin. The light absorbing agent is used to absorb light reflected from the self-etching layer in the photolithography etching process, thereby preventing problems such as undercuts, notches, and the like from appearing on the photoresist pattern. Various conventional light absorbing agents can be used as the light absorbing agent of the present invention. A representative example of a light absorbing agent is disclosed in Korean Patent Application No. 20 04-7601, the entire disclosure of which is incorporated herein by reference. Light absorbing agent is preferred

14 200921281

Its mixture. The light absorbing agent is preferably used in an amount of from 〇·1 - 30% (% by weight) to more preferably from 1 to 20% by weight based on the total amount of the composition for forming the organic anti-reflective coating. %)between. If the amount is less than 0 _ 1 % (% by weight), undercuts or notches of the resist pattern may occur due to low absorption of light reflected from the substrate. If the amount exceeds 30% (% by weight), the coating equipment will be contaminated by the fumes of the heating process 15 200921281. Since the light absorber itself has a large structure, the organic anti-reflective coating does not shrink excessively during the hardening process. In addition, light absorbing agents can also be used as a shaping agent to help the composition achieve a uniform coating, even on curved or uneven surfaces. In addition, the light absorber has good compatibility with high molecular weight materials (eg, polymers), and has excellent solubility for solvents used to form organic anti-reflective coatings, and has good reactivity with cross-linking agents. . Therefore, coating loss due to the use of a photoresist solvent can be reduced. The light absorbing agent has excellent absorbability for light emitted from the ArF-excited laser, and therefore the light absorbing agent is suitable for use on a semiconductor substrate having a high refractive index. As the solvent for forming the composition of the organic anti-reflective coating layer, a solvent capable of dissolving the compound can be used, and thus a solvent conventionally used for producing an organic anti-reflective coating can be used. Preferred solvents which can be used in the compositions of the present invention include butyrolactone, cyclopentanone, cyclohexanone, dimercaptoacetamide, dimethyl decylamine, dimethyl hydrazine, N-methylpyrrolidone, tetrahydrofuran. Alcohol, polyethylene glycol monomethyl ether (PGME), polyethylene glycol monoterpene ether acetate (PGMEA), ethyl acetate, and mixtures thereof. Preferred solvents include polyethylene glycol monoterpene ether, polyethylene glycol monomethyl ether acetate (P G Μ E A ), ethyl lactate, and mixtures thereof. The solvent is preferably used in an amount of from 30 to 99.8% by weight, more preferably from 40 to 99.8% by weight, based on the total amount of the composition for forming the organic antireflective coating. If the amount is less than 30%, the thickness of the organic anti-reflective coating may become uneven. If the dosage is higher than 99.8%, it may destroy the formed 16 1621281

The physical properties of the anti-reflective coating, such as the absorption of an exposure light. In addition, the composition for forming the organic anti-reflective coating may further comprise a cross-linking force idler, such as a cross-linking agent, a low molecular weight alcohol, an acid or acid generator, a leveling agent, an adhesion promoter, and a defoaming agent. Agents and Other Additives D To enable the formation of an organic anti-reflective coating using the compositions of the present invention, the composition is applied (plated) onto an etched layer (e.g., tantalum wafer, aluminum substrate, etc.). Conventional steps such as spin coating, roller coating, etc. are known. In addition, it is also possible to carry out the step of hardening the composition by the above-mentioned heating, so that the alkalinity of the organic solvent of the hardened organic compound is between 70 ° C and 240 ° C, if the solvent in the composition is hardened. And can not be more than 240 ° C, the composition and the rest. The method of conducting a conductor pattern may comprise forming the composition to form a hardening of the composition on the organic anti-etching layer, applying a photoresist combination layer to a predetermined pattern on the reflective coating applied to the surname layer The exposed light resisting layer is developed to form a photoresist pattern mask to engrave the organic anti-reflective pattern. Here, a conventional high temperature plate, oven, or the like for applying the above-described application composition to form and heat the bonded composition is used. Preferably, the hardening treatment does not dissolve the reflective coating in the photoresist composition solution at elevated temperatures. The preferred hardening temperature below 70 °C will not allow sufficient cross-linking to perform the cross-linking reaction. If the hardened temperature-prepared organic anti-reflective coating will become formed in the composition of the present invention in a sub-step: applying a shot coating on an etch layer; by applying the etched organic anti-reflective coating, for example The composition is heat-hardened; a photoresist layer is formed on the organic anti-object, the photoresist is exposed to light, and the exposed light is used; and the formed photoresist pattern is used as a coating layer and the etching layer. The method of forming an etch 17 200921281 organic anti-reflective coating is disclosed above. The step of forming the photoresist pattern is a conventional step and can be easily carried out by a skilled person in accordance with the composition of the present invention. For example, the photoresist composition is applied or spin-coated on the organic anti-reflective coating by a conventional method such as spin coating, and the photoresist layer can be exposed to light through a mask to form a predetermined pattern. . The step of forming the photoresist pattern may also optionally include the step of baking the light before or after the exposure process, the baking temperature being between 70 ° C and 150 ° C. If the baking temperature is 70 °C, the organic solvent in the photoresist layer cannot be sufficiently volatilized and the photo-developing agent may not be sufficiently diffused. If the baking temperature is higher than 150 °C, the acid generator may excessively diffuse to break the resolution of the pattern, and the photopolymer may become unstable. Next, the exposed photoresist layer is developed with a developer. This development step can be carried out using a conventional developing solution, using 0.1 to 10% by weight of a basic compound (e.g., potassium hydroxide, sodium carbonate, tetrahydroammonium hydroxide (TMAH)). In the next step, the formed photoresist layer is used as a mask to etch the organic anti-reflective coating and the etch layer to form the etch layer pattern. The etching step can be carried out by a conventional dry etching process. Mainly, the semiconductor element pattern is formed by etching the organic anti-reflective coating etch layer. Hereinafter, the present invention will be described by way of examples and comparative examples, but the scope of the invention is not limited to the scope of the embodiments. [Production Example 1-1] The monomer for preparing the formula 5a is as shown in the following Reaction Formula 1, and is known in the art of being equipped with a magnetic stirrer, which is low in acidity in the exposed resist layer, and the photoresist group Light I, such as hydrogen, with the button and the hair ML 18 200921281 double neck reactor, adding 30 grams (0.256 moles) of thiophenethiol of formula 2a, 27 grams (〇 _268) Methylamine (TEA) and 34 ml of tetrahydrofuran were stirred and cooled in ice water. To the cooled solution, 25.43 ml (0.253 mol) of argon-doped gas was slowly added and reacted at room temperature for about 2 hr. After the completion of the reaction, the by-product was removed by filtering the product, and the residual triethylamine and methyl propane gas were removed by washing with deionized water several times. The product was then dried over magnesium sulfate, the THF was removed under reduced pressure and the product was evaporated in vacuo to afford 25 g of compound of formula 5a. {•H-NMR: CH3 (1.93), CH (6.24, 7.5 5, 4.1 0), H (5.98, 5.49)}· [Reaction formula 1]

[Manufacturing Example 1 2 2]-_Preparation of the formula: In addition to 30 g of the compound of the formula 2b in place of 30 g of the monomer of the formula 2a, according to the method disclosed in the above Example 1-1, 2 is obtained. 8 g of the monomer of formula 5b has a yield of 93%. { 'H-NMR: CH3 (1.93), CH2 (5.41), CH (6.60, 6.72, 6.91, 6.15, 5.58)} [Production Example 1 · 3] The monomer of the formula .5c was prepared in addition to 30 g. The 2c compound was substituted for 30 g of the monomer of the formula 2a 19 200921281. According to the method disclosed in the above Example 1-1, 27 g of the monomer of the formula 5c was obtained in a yield of 90%. {h-NMR: CH3 (1_93), CH2 (4.48, 2.83), CH (6.60, 6.72, 6_91, 6.15, 5.58)}. Example 1 - 4] The monomer of the formula 5d can be obtained by the method disclosed in the above Example 1-1 except that 30 g of the compound of the formula 2a is substituted with 30 g of the compound of the formula 2d. 27 g of a monomer of the formula 5d in a yield of 83%. {]H-NMR: CH3 ( 1.93, 2.47), CH 2 (4.48, 2.83), CH (8.45), Η (6·15, 5.58)}. Manufacture Example 1-5] The monomer of formula 5e can be obtained by substituting 30 g of the compound of formula 2e with 30 g of the compound of formula 2a, according to the method disclosed in Example 1-1 above. 20 g of a monomer of the formula 5e in a yield of 60%. {]Η-ΝΜΙΙ: CH3 (1.93), Η (5·98, 5, 49)}. EXAMPLES 1-6] Preparation of a monomer of the formula 5f In addition to 30 g of the compound of the formula 2f in place of 30 g of the monomer of the formula 2a, according to the method disclosed in the above Example 1-1, 2 3 g can be obtained. The monomer of formula 5f has a yield of 77%. yH-NMR: CH3 (1.93), SH (3.0), H (5.98, 5.49)} ° [Production Example 丨-7] The monomer of the formula was prepared by substituting 30 g of the formula 2a with 30 g of the compound of the formula 2g. Monomer 20 200921281 External 'According to the method disclosed in the above Example 1-1, 25 g of a monomer of the formula 5g was obtained in a yield of 21%. "H-NMR: CH3 (1.93), CH2 (4.22), CH (6-60, 6.72, 6.91), oxime (5·89, 5.49), NH (8.0)}. ΓProduction Example 1 -8] Preparation of 戎5h monomer In addition to 30 g of the compound of formula 2h instead of 30 g of the monomer of formula 2a, '2 5 can be obtained according to the method disclosed in the above Example 1-1. The yield of the monomer of formula 5h is 70%. {iH-NMR: CH3 (1.93), CH (7.06, 7.65, 7.61), H (5.89, 5.49), NH (8.0). [Manufacturing: Example 1-9] The cover of the formula 5h is replaced by 30 g of the compound of the formula 2-i in place of the 3 g of the monomer of the formula 2a. By way of example, 25 grams of monomer of formula 5i can be obtained with a yield of 70%. {丨4 River 11: CH3 (1.93), CH2 (2.0, 2.9), Η (5·89, 5.49)}. _ [Production - Construction Example - Example 1 - 10] The preparation of the carcass of formula 5 i except that 30 g of the compound of formula 2j was substituted for 30 g of the monomer of formula 2a 'in accordance with the method disclosed in Example 1-1 above 2 6 g of a monomer of the formula 5j was obtained in a yield of 87%. pH-NMR: CH3 (1.93), CH2 (2.59), CH (6.05, 3.77), H (6.15, 5.58), OH (2.0). [Production _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the manner disclosed, 22 grams of a monomer of formula 6a was obtained in a yield of 73%. yH-NMR: CH3 (1.93), CH2 (4_52, 2.72, 2.63), H (6.15, 5.58), OH (2.0). [Manufacturing Example 1 -1 2 1 Preparation of the oxime of the formula 5h In addition to 30 g of the compound of the formula 2b in place of 30 g of the compound of the formula 2a, according to the method disclosed in the above Example 1-1, 22 was obtained. The monomer of formula 6b has a yield of 73%. UH-NMR: CH3 (1.93), CH2 (4.52, 2.72, 2.81, 2.63), H (6.15, 5.58), OH (2.0). _[Manufacturing Example 1 3] The preparation of the formula 7a is not limited to 30 g of the compound of the formula 2a in place of 30 g of the monomer of the formula 2a, according to the method disclosed in the above Example 1_1. 2 g of the monomer of formula 7a was obtained in a yield of 67%. ^H-NMR·· CH3 (1.93, 2.4 7), CH (6_97, 7, 15), H (8.98, 5.49)}.丄_制造实例1 -1 Preparation of the carcass of the formula 7b In addition to 30 g of the compound of the formula 4b in place of 30 g of the monomer of the formula 2a, 'according to the method disclosed in the above Example 1_1, 24 is obtained. The monomer yield of gram of formula 7b is 7% by weight. yH-NMR: CH3 (1.93), CH2 (4.49, 3.05), CH (7.18, 7.16, 7.02), Η (6·15, 5.58)}.丄 Manufacturing Reality Example 1 - ljj Preparation of the formula 7c! In addition to 30 grams of the compound of formula 4c in place of 30 grams of monomer of formula 2a 22 200921281, according to the method disclosed in Example 1-1 above, 24 grams of monomer of formula 7c can be obtained with a yield of 70°. /. . (ih_nmr: cH3 (1.93), CH2 (3.71), CH (7.12, 6.78), Η (5_98, 5·49)}. 丄1 造_^_例例16] __tjj^7d of the monomer except 30 In addition to the 3 gram of the compound of formula 2a, in accordance with the procedure disclosed in Example 1-1 above, a yield of 2% of the monomer of formula 7d can be obtained at 70%. {ih_nmr : CH3(1 93), CH(7 12, 7.06, 6.87), H(5_98, 5.49)}. XJji 实虚例1-17] The monomer of Jj^7e is replaced by 30g of the compound of formula 4e 3 gram of the monomer of formula 2a 'according to the method disclosed in the above Example 1-1, 2 gram of the monomer of the formula 7e can be obtained as a yield of 67%. {1h_NMr: CH3 (1.93, 2· 3 5), CH (7.68, 7.53, 7.1 2, 7.〇6, 6.87), H(5.98, 5.49), OH(5.0)}. [The preparation of the stem of formula 8a is equipped with magnetic stirring in 250 ml. In a two-necked flask, 2 g of thiophene acrylate (monomer represented by formula 5b) and 11.78 g (0.047 mol) of 2-indene acrylic acid 2 [2 (2-) were added. Hydroxyethylsulfanyl)-ethylsulfanyl]-ethyl ester (monomer represented by formula 6b), 1.59 g (0.01 mol) of AIBN and 130 ml THF. Next, the temperature of the solution was raised to 65 t, and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 1.5 liters of n-hexane 23 200921281 alkane to precipitate a product to obtain a purified reaction product solid. The obtained product was filtered. Drying can obtain 16 g of the polymer represented by the formula 8 a (yield: 5%, molecular weight = 12,800, polydispersity = 2'12). Among the polymers represented by the formulas 8 & to 8k, The ratios of A, B, C and D represent the molar percentage of individual repeating units in proportion to the individual monomers used in the polymerization reaction. [Equation 8a]

f Example 1-2] Preparation of a polybenzidine of formula 8b In a 250 ml two-necked flask equipped with a magnetic stir bar, 17 78 g (0.109 mol) of porphyrin methacrylate (the monomer represented by the formula) was added. 〉, 3.02 g (0.012 mol) of 2_methacrylic acid 2 [2(2-hydroxyethylsulfanyl)_ethylsulfanyl]-ethyl ester (monomer represented by formula 6b), 251 g (〇〇) 12 moles of 2-mercaptosulfanylphenyl 2-methacrylate (monomer represented by Formula 7a), 1.17 g (0.007 mol) of AIBN, and 1 mL of THF. Next, The temperature of the solution was raised to 65 ° C. and reacted for about 24 hours. After the reaction was completed, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. The obtained product was filtered and dried to obtain hydrazine. 4 g of the polymer represented by the formula 8b (yield: 60%, molecular weight = 13 500, polydispersity = 2 08). 24 200921281 [Formula 8b]

ΓExample 1-3] Preparation of polymer of formula 8c In a 250 ml two-necked flask equipped with a magnetic stir bar, 20 g (0.11 mol) of thiophene acrylate (form represented by formula 5a) was added. , 9.16 g (0.037 mol) of 2-indole 2-[2(2-hydroxyethylsulfanyl)-ethylsulfanyl]-ethyl ester (monomer represented by formula 6b), 4.57 g (0.022 mol) of 2-mercaptothioalkylphenyl 2-mercaptoacrylate (monomer represented by Formula 7a), 1.69 g (0.01 mol) of AIBN, and 100 ml of THF. Next, the temperature of the solution was raised to 65 ° C and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. The obtained product was filtered and dried to obtain 18 g of a polymer represented by the formula 8c (yield: 53%, molecular weight = 15,000, polydispersity = 2.22). [Equation 8c]

25 200921281 丄Example 4 4] ^ compound in a 250 ml double-necked view with magnetic sandalwood, add 19.02 qing " ear 2-methyl acrylate 2 ♦ ... _ 5 _ base) 5d represented by the monomer), 7.51g (〇〇3 mole) of 2_methyl acrylate 2 --ethyl thiol)- ethane thiol] _ B 8 (represented by the formula Monomer), 4.W18 Molar) 2_? propyl propylene 2 phenyl thiophene aryl (Formula 7: represented monomer), h53 g (G (10) 9 mol) of A · and 1 00 Pen liters of THF. Then, the solution temperature was raised to 65 ° C and the reaction was carried out for about 24 hours. After the reaction is completed, it is poured into a 1 liter liter of the hexidine to make the product sink, and the purified reaction product solid can be obtained. The obtained product was filtered and dried to obtain 16 g of a polymer represented by the formula 8d (yield: 52%, molecular weight = 14,300, polydispersity = 2.20).

_!实_施_1卜5] Prepared in a 250 ml two-necked flask equipped with a magnetic pick-up, adding i8 〇3 g (0.090 mol) of 2-mercaptothioacrylic acid s_(5_曱Thiathiazol-2-yl) vinegar (monomer represented by formula 5e), 7.51 g (0_03 mol) of 2-methylpropanate 2-[2(2-ethylthio)-ethyl sulphide Ethyl acetate (monomer of formula 26 200921281), 4_0 g (0.018 mol) of 2-phenylthioalkyl 2-methacrylate (monomer represented by formula 7b), 1.48 g (0.009 mol) of AIBN and 100 ml of THF. Next, the temperature of the solution was raised to 65 (>c, and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 1 Torr of n-hexane to precipitate the product to obtain a purified reaction product solid. The obtained product was filtered. Drying can obtain 13 g of the polymer represented by the formula 8e (yield: 44%, molecular weight = 1,200, polydispersity = 2.10). [Equation 8e]

[Example 1-6] Preparation of a polymerized oxime of the formula 8f In a 250 ml two-necked flask equipped with a magnetic stir bar, 19 65 g (0.090 mol) of 2-methylthioacrylic acid s_(5-hydrogen sulfide) was added. 2-thiazol-2-yl)ester (monomer represented by formula 5f), 5 71 g (〇〇3 mol) of 2-[2-(2-hydroxyethylsulfanyl) 2-methacrylate _ ethanethioalkyl] _ ethyl ester (monomer represented by formula 6a), 4·5 gram (〇·018 mol) of 2-mercaptoacrylic acid 2 ketone-2,3_dihydro cumene [1] 4] dioxene-7-yl ester (monomer represented by formula 7c), 1.49 g (0.009 mol) of AIBN, and 1 ml of THF. Next, the temperature of the solution was raised to 65 ° C and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 10 liters of n-hexane to precipitate a product, and a purified reaction product was obtained. Polymer (yield [Formula 8f] The obtained product was filtered, dried, and yield: 57% 'molecular weight = 13,5 〇〇, f · 17 g of polydispersity represented by the formula 8f = 2.28).

[Examples 1 to 7] Polymers of the f-type formula were placed in a 250 ml two-necked flask equipped with a magnetic stirrer, and 丨6 3 ^ g (0.090 mol) of 2-thiophenylmethylamine oxime acrylic acid was added. Ester (monomer represented by formula 5g), 5.71 g (〇_〇3 mol) of 2-methacrylic acid 2-[2-(2-ethylthioalkyl)-ethionyl]-ethyl ester ( a monomer represented by the formula 6a), 4 5 g (〇〇i8 mol) of 2-keto-2-keto-2-yl-2,3-dihydrobenzo[ι,4]dioxin_7_A ester ( Monomer represented by Formula 7c), 1.33 g (0.009 mol) of Aibn, and 100 ml of THF. Next, raise the temperature of the solution to 65 ° C and anti-deer for about 24 hours. After the reaction is completed, it is poured into 1 · liter of liter of n-hexane to precipitate a product, and a purified reaction product solid can be obtained. The obtained product was subjected to drying and drying to obtain 19 g of a polymer represented by the formula 8 g (yield: 72%, molecular weight = 11,500, polydispersity = 2.25). 28 200921281 [Formula 8g]

In a two-necked flask equipped with a magnetic stirrer, add 18.92 g (0.090 mol) of thioglycolic acid Ν 曱 曱 propyl propyloxy) (the military represented by the formula π), 5.71 g (〇〇3 mole) 2-[2-(2-hydroxyethylsulfanyl)-ethylsulfanyl]-ethyl ester (a monomer represented by the formula & 4.87 g (0.018 mol) of 2-phenyl thioglycolyl methacrylate (monomer represented by formula 7d), 47.47 g (0.009 mol) of AIBN and 100 ml of THF. Next, the temperature of the solution was raised to 65 ° C, and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. Drying gave 16 g of the polymer represented by the formula 8h (yield: 54% 'molecular weight = 1,800, polydispersity = 2.08). [Equation 8h]

29 200921281 [Examples 1 to 9] Preparation of a polymer of the formula 8i In a 250 ml two-necked flask equipped with a magnetic stir bar, 1,6.8 g (0.090 mol) of 2-mercaptothiopropanol was added. Acid S-(4,5-dihydro-thiazol-2-yl) ester (monomer represented by formula 5i), 5.71 g (0.03 mol) of 2-[2-(2-hydroxyl) 2-methyl acrylate Ethylsulfanyl)-ethionyl]-ethyl ester (monomer represented by formula 6a), 4.87 g (0.018 mol) of 2-phenylsulfanyl 2-methyl methacrylate (Formula 7d) The monomer represented), 1.37 g (0.008 mol) of AIBN and 100 ml of THF. Next, the temperature of the solution was raised to 65 ° C and the reaction was carried out for about 24 hours. After the reaction was completed, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. The obtained product was filtered and dried to obtain 14 g of a polymer represented by the formula 8i (yield: 51%, molecular weight = 15,600, polydispersity = 2.28). [Equation 8i]

[Example 1 - 1 0 1 Preparation of the polymer of the formula 8 i In a 250 ml two-necked flask equipped with a magnetic stir bar, 1 9 · 8 3 g (0.090 mol) of 2-mercaptopropylcarboxylate was added. Acid 5-hydroxy-[1,4]dithiazolidin-2-yl ester (monomer represented by formula 5j), 5.71 g (0.03 mol) of 2-mercaptoacrylic acid 2-[2-(2-hydroxyl) Ethylsulfanyl)-ethionyl]-ethyl ester (monomer represented by formula 6a)' 6.24 g (0-018 mol) of 2-methyl methacrylate 4-(4-hydroxy- 3- 30 200921281 A 2-phenylsuccinyl) 2-methyl streptoester (monomer represented by formula 7e), 159 g (0.010 mol) of AIBN and 1 ml. The solution temperature was then increased to 6 rc ' and reacted for about 24 hours. After the reaction was completed, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. The obtained product was filtered and dried to obtain 18 g of a polymer represented by the formula (yield: 57%, molecular weight = 14,5 〇〇, polydispersity = 2 32). [Formula 8j]

[f. Example 8k nucleus in a 250 ml two-necked flask equipped with a magnetic stirrer, adding ι 983 g (0·090 mol) of 2-mercaptopropionic acid 5-hydroxy-[1,4 Dithiazolidine-2-yl 6 (monomer represented by formula 5j), 7 51 g (〇〇12 mol) of 2-[2-(2-hydroxyethylsulfanyl) 2-methacrylate )-ethylthioalkyl]-ethyl ester (monomer represented by the formula), 6.24 g (〇.018 mol) of 2_mercaptoacrylic acid 4_(4-hydroxy-3-methylphenylsulfanyl) 2_methyl stupyl ester (monomer represented by formula 7e), 8 g (0.010 mol) of Aibn, and 1 ml of thf. Next, raise the solution temperature to 65. . ' And react about 24 hours. After completion of the cis reaction, it was poured into 1.0 liter of n-hexane to precipitate a product, and a purified reaction product solid was obtained. The obtained product was filtered and dried to obtain 318 g of the formula represented by the formula 8 k 31 200921281 polydispersity = 2.18). 63% ‘ molecular weight=14,9〇〇

Polymer (yield [formula 8k] machine antireflection j as shown in Table 1, 〇.13 g of the polymer of the example "...-η (combination of the formula Q ▼ ^^ (formula a 8k), 0.06 g of the cross-linking agent represented by the formula 9a_9c, the light absorbing agent of the formula 〇 gram of 〇 gram, the acid generator represented by the formula of 0.01 g, and 137 g of propylene glycol monoethyl ether acetate (pGMEA) are obtained. A composition for forming an organic anti-reflective coating. The composition for forming an organic anti-reflective coating is applied in a spin coating manner to a tantalum wafer substrate to produce an organic anti-reflective coating having a thickness of about Α0 Α. And baked at 24 〇t for 9 sec. The refractive index (η: actual part) and absorptivity (k: hypothetical part) of the organic anti-reflective coating produced by the EUipsometer measurement are shown in Table 1. In addition, after measuring the thickness of the organic anti-reflective coating, 'the layer was immersed in pgmea for about 60 seconds' and spin-coated at 2 rpm for about 3 sec seconds and heated at i 〇 (rc for about 60 seconds). The thickness of the organic anti-reflective coating was measured again and it was found that the thickness of the organic anti-reflective coating was not degraded. 32 200921281 <Table 1> Polymer r Crosslinker acid generator coefficient (n) Absorbance (k) Example 2-1 Formula 8 a Formula 9a Formula 11a 1 .92 0.28 Example 2-2 Formula 8b Formula 9 a 11a 1.90 0.30 Example 2-3 Equation 8 c Equation 9 a TAG-2 1 72 1.93 0.27 Example 2-4 Formula 8d Equation 9a TAG-227 8 1.89 0.28 Example 2-5 Equation 8 e Equation 9b Equation lib 1.93 0.26 Example 2-6 Formula 8f Formula 9b Formula 11a 1.90 0.22 Example 2-7 Formula 8g Formula 9b TAG-227 8 1 .86 0.27 Example 2-8 Formula 8h Formula 9b TAG-2 1 72 1.94 0.30 Example 2 9 Equation 8i Equation 9 c Equation 11a 1.92 0,32 Example 2-10 Equation 8j Equation 9 c TAG-227 8 1.96 0.30 Example 2-11 Equation 8k Equation 9c TAG-2 1 72 1 .94 0.2 7 In Table 1 Among them, the TAG compound (TAG-2 1 72, TAG-2278, etc.) represents an acid generator of the dodecylbenzene acid type (manufacturer: King Industry).

H3c〇^ Factory 〇CH3 N丫N 〇=< I >=〇

N into N

H3co

Och3 33 200921281 [Formula 9b [Equation 9c]

MeO MeO·

MeO OMe V N N, N N"^N〆 OMe OMe [Formula 10 a

Me〇,

MeCr 9^3 C!H;3rQ-pH3'- Φ

0:H RINIR H®

R θ π O-S—CF3 Ο b

34 200921281 It can be seen from Table 1 that the BRAC layer formed by the composition of the present invention has an excellent refractive index (n) and an alkene yield (k), and has extremely small thickness and loss and desirable peeling resistance. In general, at a specific wavelength, when the value of k is decreased (k < 0 '2) ', standing waves, undercuts, notches, and the like are generated due to uneven reflection of light. Therefore, the shape of the photoresist pattern will be destroyed. Conversely, when the value of k is raised (k > 0 7), the absorption rate is excessively increased, which will destroy the photosensitivity of the photoresist. Therefore, the manufacturing efficiency of the semiconductor is destroyed. At the same time, when the value of η increases (n > 1.8), the thickness of the BRAC layer decreases, so a finer L/S pattern (45 nm) can be generated than the current L/s pattern (65 nm). Thus, a BRAC layer made with the composition of the present invention can be used in an ArF impregnation process. Conversely, when the value of n decreases (n < 14), the thickness of the organic anti-reflective coating must be increased, resulting in a decrease in the surname rate. 35

Claims (1)

200921281 X. Patent Application Range: 1. A polymer for forming an organic anti-reflective coating comprising a repeating unit represented by Formula 1, [Formula 1] Wherein Ri is a hydrogen atom or a methyl group (-CH3), R2 is S, hydrazine or NH, and R4 is a group having a hydroxyl group (-OH). 2. The polymer of claim 1, wherein the R4 is Freedom of choice H 0-* P= GI is composed of groups. 3. The polymer of claim 1, wherein the molar percentage of the repeating unit of Formula 1 is between 1 and 99 mol% compared to the total repeating unit constituting the polymer. 4. The polymer of claim 1, wherein the polymer has a structure as shown in Formula 1a, 36 200921281 [Formula la], R1 ( , \ / \ R2 R3 尺4 R5 wherein each R is hydrogen or methyl (-CH3); each R2 is S, hydrazine or NH; R3 is a heterocyclic group containing sulfur; and R4 is a hydroxyl group (-OH) a group having a phenyl group; and a, b, and c represent the molar % of the individual repeating units compared to the total repeating unit constituting the polymer, and are 1 to 9 8 respectively Mohr%, 1~9 8 mol% and 1~9 8 mol%. 5. The polymer of claim 4, wherein R 3 is a C 3 -CIO heterocyclic group containing sulfur, R 4 is a hydrogen group of CrCzo having a hydroxyl group (-0H), and R 5 is A C6 to C20 hydrocarbon group having a phenyl group. 6. A composition for forming an organic anti-reflective coating comprising: 0.1% to 6.9% (% by weight) of a polymer comprising a repeating unit of Formula 1; =〇 wherein, the heart is a hydrogen atom or a fluorenyl group (-CH3), R2 is S, 0 or NH, and R4 is a group having a hydroxyl group (-OH); 37 200921281 0· 1 %~3 0% (% by weight a light absorbing agent for absorbing an exposure light; and 30% to 99.8% by weight of an organic solvent for dissolving the polymer. 7. The composition of claim 6, wherein the light absorption ch3 The CHs collector is selected from the following compounds, including Φ CH^-CKg cH* CH3 38 200921281 8. The composition of claim 6, wherein the solvent is selected from the group consisting of butyrolactone, cyclopentanone, cyclohexanone, dimethylacetamide, dimethylformamide Nitrogen I, N-decylpyrrolidone, tetrahydrofuranol, polyethylene glycol monomethyl ether (PGME), polyethylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, and mixtures thereof. 9. A method for forming an organic anti-reflective coating comprising the steps of: applying a composition to an etch layer, the composition comprising: 0.1% to 69.9% (% by weight) of one of Formula 1 Polymer of repeating unit, [Formula 1] F=〇39 200921281 wherein, Ri is a hydrogen atom or a fluorenyl group (-CH3), R2 is S, 0 or NH, and R4 is a group having a hydroxyl group (-OH); 0.1% to 3 0% (% by weight) a light absorbing agent for absorbing an exposure light; 30% to 99.8% by weight of an organic solvent for dissolving the polymer; and hardening the applied composition by heating. 40 200921281 VII. Designated representative map: (1) The representative representative of the case is: None. (2) The representative symbol of the representative figure is a simple explanation: The time: the chemistry of the chemical chemistry, the case of the singularity, the singularity of the singularity, the most obvious RIR 4