KR20190134389A - Organic hard mask composition for anti-reflection and method of forming patterns using the composition - Google Patents

Abstract

The present invention relates to an anti-reflective composition for an organic hard mask comprising a polymer represented by chemical formula 1 and an organic solvent, and to a pattern forming method using the same.

Description

Composition for antireflection organic hard mask and pattern formation method using same {ORGANIC HARD MASK COMPOSITION FOR ANTI-REFLECTION AND METHOD OF FORMING PATTERNS USING THE COMPOSITION}

The present invention relates to a composition for an antireflective organic hard mask having antireflection film properties useful in a lithographic process, comprising a polymer containing an aromatic amine and a composition for an antireflection organic hard mask comprising the same, and pattern formation using the same. It is about a method.

In recent years, highly integrated designs due to miniaturization and complexity of electronic devices have accelerated the development of more advanced materials and related processes, thus lithography using existing photoresists also requires new patterning materials and techniques. It became.

In the patterning process, in order to transfer the fine pattern of the photoresist to the substrate to a sufficient depth without collapse phenomenon, an organic film called a hard mask layer (hard mask layer) may be formed.

The hard mask layer serves as an interlayer that transfers the fine pattern of the photoresist to the material layer through a selective etching process. Therefore, the hard mask layer needs properties such as heat resistance and etching resistance to withstand multiple etching processes.

On the other hand, it has recently been proposed that the hard mask layer is formed by a spin-on coating method instead of a chemical vapor deposition (CVD) method. The spin-on coating method is not only easy to process but can also improve gap-fill and planarization properties.

In general, the corrosion resistance is in conflict with the spin-on characteristics, and an organic film material capable of satisfying both of these properties is required.

The present invention relates to a new organic hardmask material having sufficient etching resistance and excellent solubility in such an organic hardmask material.

The two properties required for the organic hardmask layer, the solubility and the etching resistance, are in a mutually conflicting relationship, and a composition for an antireflective organic hardmask that can satisfy both of them is required. The materials introduced in the semiconductor lithographic process while satisfying the characteristics of such organic hardmask materials have recently been introduced (Patent 10-1497132, 10-1590810, 10-1590809, 10-1752833, 10-1848343, 10-1804258, 10). -1810610, 10-1829750, 10-1684978, Published Patent 10-2016-0110657, 10-2017-0087294 and the like), which is an organic hard using a copolymer having an appropriate polymer molecular weight using hydroxypyrene Mask materials.

The present invention is to solve the above problems of the prior art, an anti-reflective composition having high etching selectivity, sufficient resistance to multi-etching, and minimizes the reflectivity between the resist and the back layer It is an object of the present invention to provide a novel anti-reflective organic hard mask composition that can be used to perform lithographic techniques using a pattern forming method using the same.

The antireflective organic hard mask composition according to the embodiment of the present invention includes a polymer represented by the following Chemical Formula 1 and an organic solvent.

[Formula 1]

In Chemical Formula 1,

Ar ₁ is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amidino, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted Or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C10 alkoxy group, substituted or unsubstituted C3 to C10 cycloalkyl group, substituted or unsubstituted C2 to C10 heterocycloalkyl group, substituted or Unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, or Combination of these,

X is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

Y is a C1 to C20 alkylene group substituted with at least one hydroxyl group, a C6 to C30 arylene group substituted with at least one hydroxyl group, a C2 to C30 heteroaryl group substituted with at least one hydroxyl group, or a combination thereof ,

Z1 to Z3 each have a range between Z1 / (Z1 + Z2 + Z3) = 0.05 to 0.45, Z2 / (Z1 + Z2 + Z3) = 0.5, Z3 / (Z1 + Z2 + Z3) = 0.05 to 0.45 ,

“Substituted” herein means that the hydrogen atom is substituted with a C1 to C5 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a combination thereof.

In Formula 1, Ar ₁ may be any one selected from substituents listed in the following Group 1.

[Group 1]

In Formula 1, X may be any one selected from the substituents listed in Group 2 below.

[Group 2]

In Formula 1, Y may be any one selected from the substituents listed in Group 3 below.

[Group 3]

The weight average molecular weight (Mw) of the polymer may be 1,000 to 30,000.

The antireflective organic hard mask composition according to one embodiment may further include a crosslinking agent and an acid catalyst.

The crosslinking agent may be at least one selected from the group consisting of melamine resin, amino resin, glycoluril compound, and bisepoxy compound.

The acid catalyst is p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzo At least one selected from the group consisting of intosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

The antireflective organic hardmask composition according to one embodiment comprises 1 to 20 wt% of the polymer, 0.1 to 5 wt% of the crosslinking agent, 0.001 to 0.05 wt% of the acid catalyst and 74.95 to 98.899 wt% of the organic It may include a solvent.

According to the present disclosure, it is possible to minimize the reflectivity between the resist and the backing layer by having a refractive index and absorbance in a useful range as an antireflection film in the UV short wavelength region such as ArF (193 nm) and KrF (248 nm) when forming a film. In the lithographic process compared to the mask, the etching selectivity is high, so that the resistance to multiple etching is sufficient, thereby providing an antireflective organic hard mask composition having an excellent pattern evaluation result and a pattern forming method using the same.

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

According to the present invention, there is provided a composition for antireflection organic hard mask comprising a polymer represented by the following formula (1) and an organic solvent.

[Formula 1]

In Chemical Formula 1,

Ar ₁ is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amidino, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted Or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C10 alkoxy group, substituted or unsubstituted C3 to C10 cycloalkyl group, substituted or unsubstituted C2 to C10 heterocycloalkyl group, substituted or Unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, or Combination of these,

X is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,

Y is a C1 to C20 alkylene group substituted with at least one hydroxyl group, a C6 to C30 arylene group substituted with at least one hydroxyl group, a C2 to C30 heteroaryl group substituted with at least one hydroxyl group, or a combination thereof ,

Z ₁ to Z ₃ are each Z ₁ / (Z ₁ + Z ₂ + Z ₃ ) = 0.05 to 0.45, Z ₂ / (Z ₁ + Z ₂ + Z ₃ ) = 0.5, Z ₃ / (Z ₁ + Z ₂ + Z ₃ ) = 0.05 to 0.45,

“Substituted” herein means that the hydrogen atom is substituted with a C1 to C5 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a combination thereof.

In this case, in Formula 1, Ar ₁ may be any one selected from the substituents listed in the following Group 1.

[Group 1]

X of the general formula (1) is mainly made by combining a co-monomer component that can proceed one-to-one polymerization with an aromatic ring compound under acid (acid) catalyst conditions, and the solubility of the polymer material formed in the solvent Polymerized linkage group (linkage group) to have a role to increase each independently have the form as shown below. It is mainly a compound having an aldehyde form such as paraformaldehyde, benzaldehyde, or the like, or a dimethoxy, di-ethoxy group, and prepared by reacting with the carbazole derivative under an acid catalyst.

For example, in Formula 1, X may be any one selected from substituents listed in Group 2 below.

[Group 2]

Meanwhile, Y in Chemical Formula 1 is an aryl group compound having a different hydroxyl group (OH), and is mainly introduced to improve thermosetting reactivity and etching selectivity of the entire polymer structure.

For example, in Formula 1, Y may be any one selected from substituents listed in Group 3 below.

[Group 3]

At this time, the thing not represented by the hydroxyarylene mentioned in the group 3 means the formation of a conventional hydroxyarylene structure.

The weight average molecular weight (Mw) of the polymer may be 1,000 to 30,000. The weight average molecular weight may be a polystyrene reduced average molecular weight measured using gel permeation chromatography.

By the polymer having a weight average molecular weight in the above range it can be optimized by adjusting the solubility in the organic solvent of the composition for an antireflective organic hard mask comprising the polymer. As described above, the polymer according to one embodiment is optimized for solubility in organic solvents and stable to organic solvents, so that the composition for an antireflective organic hard mask including the polymer may be, for example, a photoresist underlayer material. When used, it is possible to minimize the generation of by-products due to peeling by the solvent or the generation of chemicals during the process for forming the photoresist pattern, it is possible to minimize the thickness loss by the upper photoresist solvent.

The organic solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the polymer, for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) Monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, methylpyrroli At least one selected from don, methylpyrrolidinone, acetylacetone and ethyl 3-ethoxypropionate.

Meanwhile, the antireflective organic hard mask composition may further include a crosslinking agent and an acid catalyst. The crosslinking agent is preferably capable of crosslinking the repeating units of the polymer by heating in a reaction catalyzed by the generated acid, and the acid catalyst is preferably an acid catalyst which is thermally activated.

More specifically, the crosslinking agent is not particularly limited as long as it is a crosslinking agent that can react with the hydroxyl group of the aromatic ring-containing polymer in a manner that can be catalyzed by the generated acid.

For example, the crosslinking agent may be at least one selected from the group consisting of melamine resin, amino resin, glycoluril compound, and bisepoxy compound. More specifically, the crosslinking agent is an etherified amino resin such as methylated or butylated melamine resin (specifically, methylated melamine and butylated melamine resin) and methylated or butylated urea resin (Urea Resin). (Examples include Cymel U-65 Resin or UFR 80 Resin), glycoluril compounds (specifically, Powderlink 1174), or bisepoxy compounds (specifically, resorcinol diglycidyl ether) It may be any one selected from the group containing, or a combination thereof.

As the acid catalyst used in the antireflective organic hard mask composition of the present invention, an organic acid such as p-toluenesulfonic acid monohydrate may be used, and a thermal acid generator having a storage stability may be used. , TAG) -based compounds may be used as a catalyst. Thermal acid generators are acid generator compounds that are intended to release acids upon thermal treatment, for example, pyridinium P-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadiene On, benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids.

As another example, the acid catalyst may be p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexa Dienone, benzoin tosylate, 2-nitrobenzyl tosylate, and an alkyl ester of organic sulfonic acid, or any combination thereof.

Meanwhile, the antireflective organic hard mask composition includes 1 to 20 wt% of the polymer, 0.1 to 5 wt% of the crosslinking agent, 0.001 to 0.05 wt% of the acid catalyst, and 74.95 to 98.899 wt% of the organic solvent. can do.

The antireflective organic hard mask composition according to one embodiment uses 1 to 20% by weight of the polymer, for example, 3 to 15% by weight of the polymer, and 0.1 to 5% by weight of the crosslinking agent, for example, 0.1 to 3 By weight of the cross-linking agent, it can be made up to a total of 100% by weight of the acid catalyst 0.001 to 0.05% by weight, for example, 0.001 to 0.03% by weight of the acid catalyst, and the remaining components using an organic solvent, for example , 74.95 to 98.899% by weight of the organic solvent.

At this time, when the polymer is less than 1% by weight or more than 30% by weight, it becomes less than or exceeds the desired coating thickness, so that it is difficult to match the exact coating thickness.

When the crosslinking agent is less than 0.1% by weight, the crosslinking property may not appear, and when the amount of the crosslinking agent is greater than 5% by weight, the optical properties of the coating film may be changed by the excessive input.

In addition, when the acid catalyst is less than 0.001% by weight crosslinking properties may not appear well, and when the acid catalyst exceeds 0.05% by weight may increase the acidity due to excessive input may affect the storage stability.

The antireflective organic hard mask composition according to one embodiment has a refractive index and absorbance of a useful range as an antireflection film in a UV short wavelength region such as ArF (193 nm) and KrF (248 nm) when forming a film, thereby reflecting between the resist and the back layer. In addition, the etching selectivity in the lithographic process is higher than that of the conventional organic hard mask, thereby improving resistance to multiple etching.

Hereinafter, the present invention will be described in more detail with reference to the synthesis of the polymer described above and the preparation of an antireflective organic hard mask composition comprising the same. However, the following examples are not intended to limit the technical scope of the present invention.

Synthesis Example

Synthesis Example 1-1) Preparation of 2- (8-bromonaphthalen-1-yl) aniline

In the reactor, 10.0 g of 2-aminophenylboronic acid, 22.97 g of 1,8-dibromonaphthalene, tetrakis (triphenylphosphine) palladium (0) tris (dibenzylideneacetone) dipalladium (0) After addition, 200 mL of dimethylformamide was added. 170 mL of 2M aqueous potassium carbonate solution was added dropwise to the reaction mixture. The reaction mixture was raised to 80 ° C. and stirred. After the reaction was completed, the reaction mixture was cooled to room temperature, and 400 mL of ethyl acetate was added thereto. The organic layer was taken and washed with 100 mL of purified water. 10 g of anhydrous magnesium sulfate was added to the organic layer, followed by stirring for 30 minutes. The organic layer was filtered and concentrated under reduced pressure. The concentrated residue was subjected to silica gel chromatography (hexane / dichloromethane = 3/1) to give 2- (8-bromonaphthalen-1-yl) aniline. (12.24 g, Yield 56.2%) MS: [M] = 298.

Synthesis Example 1-2) Preparation of 7H-benzo [kl] acridine

10.0 g of 2- (8-bromonaphthalen-1-yl) aniline, 2.83 g of tris (dibenzylideneacetone) dipalladium (0), 11.28 g of sodium tert-butoxide and tris tert-butylphosphonium tetra in the reactor 0.90 g of fluoroborate was added followed by 200 mL of toluene. The reaction mixture was heated to reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 200 mL of ethyl acetate was added thereto. The organic layer was taken and washed with 100 mL of purified water. Anhydrous magnesium sulfate 5g was added to the organic layer, followed by stirring for 30 minutes. The organic layer was filtered and concentrated under reduced pressure. The concentrated residue was subjected to silica gel chromatography (hexane / ethyl acetate = 4/1) to give 7H-benzo [kl] acridine. (4.85 g, yield 66.5%) MS: [M] = 217.

Synthesis Example 1-3) Preparation of 7-phenyl-7H-benzo [kl] acridine

5.03 g of bromobenzene bromophenyl and 7.66 g of 7H-benzo [kl] acridine, 2.70 g of tris (dibenzylideneacetone) dipalladium (0), 10.78 g of sodium tert-butoxide and tris tert-butyl 0.86 g of phosphonium tetrafluoroborate was added followed by 200 mL of toluene. The reaction mixture was heated to reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and 400 mL of ethyl acetate was added thereto. The organic layer was taken and washed with 200 mL of purified water. 15 g of anhydrous magnesium sulfate was added to the organic layer, followed by stirring for 30 minutes. The organic layer was filtered and concentrated under reduced pressure. The concentrated residue was subjected to silica gel chromatography (hexane / ethyl acetate = 4/1) to give 7-phenyl-7H-benzo [kl] acridine. (5.10 g, Yield 58%) MS: [M] = 293

Synthesis Example 1-4) Other Synthesis

As a result of reacting the reactants described in Table 1 in the same manner as in Synthesis Examples 1-1 to 1-3, the yield and MS of Table 1 were obtained with respect to A-8 in the resulting product A-1.

Product short name Reactant product Yield
(%) MS:
[M] A-1

54 369 A-2

55 343 A-3

52 393 A-4

45 393 A-5

50 418 A-6

53 410 A-7

52 534 A-8

51 532

Synthesis Example 2-1) Synthesis of benzo [kl] acridine-based cyclic polymer

In a 250 mL round flask, 29.3 g (100 mmol) of 7-phenyl-7H-benzo [kl] acridine, 6.4 g (200 mmol) of paraformaldehyde, and 1 Dissolve 14.4 g (100 mmol) of naphthol (1-naphthol) in 107 g of propylene glycol monomethylether acetate (PGMEA), and then add 0.8 g of sulfuric acid stock solution.

The molecular weight is measured using GPC in the middle of the reaction while the polymerization is carried out while maintaining the reaction temperature at about 120 ° C.

After reacting for about 12 hours, the reactant is dropped in an excess of methanol / water (9: 1) cosolvent, and then the resulting solid is dissolved in an appropriate amount of PGMEA solvent, and then excess ethanol / water (9: 1) Drop into cosolvent to catch sediment.

The resulting solid was dried in a vacuum oven at about 50 ° C. for about 20 hours, whereby a weight average molecular weight (Mw) 2,700 polymer was obtained.

Synthesis Example 2-2 Synthesis of benzo [kl] acridine-based cyclic polymer

17.6 g (60 mmol) of 7-phenyl-7H-benzo [kl] acridine and 20 g (120 mmol) of 1,4-Bis (methoxymethyl) benzene (MBB), and 8.7 g (60 mmol) of 2-naphthol is dissolved in 102 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of sulfuric acid stock solution is added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 2,900 polymer.

Synthesis Example 2-3) Synthesis of benzo [kl] acridine-based cyclic polymer

17.6 g (60 mmol) of 7-phenyl-7H-benzo [kl] acridine, 13 g (120 mmol) of benzaldehyde, and 8.7 g (60 mmol) of 1-naphthol Was dissolved in 93 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of sulfuric acid stock solution was added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 2,800 polymer.

Synthesis Example 2-4) Synthesis of benzo [kl] acridine-based ring polymer

15.7 g (40 mmol) of 7- (phenanthrenphenyl-9yl) -7H-benzo [kl] acridine (7- (phenanthren-9-yl) -7H-benzo [kl] acridine) of A-3 and benzaldehyde 11 g (100 mmol) of benzaldehyde and 8.7 g (60 mmol) of 1-naphthol are dissolved in 79 g of propylene glycol monomethyl ether acetate (PGMEA), followed by 0.4 g of sulfuric acid stock solution.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight 3,100 polymer.

Synthesis Example 2-5) Synthesis of benzo [kl] acridine-based ring polymer

75.1 ((pyren-1-yl) -7H-benzo [kl] acridine) 25.1 g (60 mmol) and benzaldehyde of A-5 13 g (120 mmol) of benzaldehyde and 13 g (60 mmol) of 1-pyrenol are dissolved in 93 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of sulfuric acid stock solution is added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 2,800 polymer.

Synthesis Example 2-6) Synthesis of benzo [kl] acridine-based cyclic polymer

7-([1,1'-biphenyl] -4-yl) -7H-benzo [kl] acridine (7-([1,1'-biphenyl] -4-yl) -7H of A-1 22.1 g (60 mmol) of benzo [kl] acridine, 13 g (120 mmol) of benzaldehyde, and 13 g (60 mmol) of 1-pyrenol were dissolved in 107 g of propylene glycol monomethyl ether acetate (PGMEA). To this, 0.5 g of sulfuric acid stock solution is added.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 3,000 polymer.

Synthesis Example 2-7) Synthesis of benzo [kl] acridine-based ring polymer

25.1 g (60 mmol) of 7- (pyren-1-yl) -7H-benzo [kl] acridine of A-5, 4.3 g of paraformaldehyde, and 13 g (60 mmol) of 1-pyrenol Was dissolved in 93 g of propylene glycol monomethyl ether acetate (PGMEA), and 0.5 g of sulfuric acid stock solution was added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight 3,100 polymer.

Synthesis Example 2-8) Synthesis of benzo [kl] acridine-based cyclic polymer

20.9 g (50 mmol) of 7- (pyren-1-yl) -7H-benzo [kl] acridine of A-5, 3.6 g of paraformaldehyde, and 9,9-bishydroxyphenylflurin {9, 17.5 g (50 mmol) of 9-Bis (4-hydroxyphenyl) fluorine} was dissolved in 93 g of propylene glycol monomethyl ether acetate, and then 0.4 g of sulfuric acid stock solution was added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 3,000 polymer.

Synthesis Example 2-9) Synthesis of benzo [kl] acridine-based cyclic polymer

25.1 g (60 mmol) of 7- (pyren-1-yl) -7H-benzo [kl] acridine of A-5, 20 g (120 mmol) of 1,4-Bis (methoxymethyl) benzene (MBB), and 1- 13 g (60 mmol) of pyrenol are dissolved in 130 g of propylene glycol monomethyl ether acetate, and 0.5 g of sulfuric acid stock solution is added thereto.

After the polymerization in the same manner as in Synthesis Example 2-1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 2,700 polymer.

Synthesis Example 2-10) Synthesis of benzo [kl] acridine-based cyclic polymer

20.6 g (60 mmol) of 7- (naphthalen-1-yl) -7H-benzo [kl] acridine (7- (naphthalen-1-yl) -7H-benzo [kl] acridine) of A-2 and 1, 20 g (120 mmol) of 4-bismethoxymethylbenzene (MBB) and 13 g (60 mmol) of 1-pyrenol are dissolved in 119 g of propylene glycol monomethyl ether acetate, and 0.5 g of sulfuric acid stock solution is added thereto.

After the polymerization in the same manner as in Preparation Example 1, the polymer was purified and dried in a vacuum oven to obtain a weight average molecular weight of 2,700 polymer.

Comparative Synthesis Example) Polymer Synthesis According to Comparative Synthesis Example

4,4 '-(9H-fluorene-9,9-diyl) diphenol (4,4'-(9H-fluorene-9,9-diyl) diphenol) 35 g (100 mmol) and 11 g (100 mmol) benzaldehyde ) Is dissolved in 110 g of PGMEA, and then 1 g of concentrated sulfuric acid is added thereto.

The molecular weight is measured using GPC in the middle of the reaction while the polymerization is carried out while maintaining the reaction temperature at about 120 ° C.

After reacting for about 12 hours, the reactant is dropped in an excess of methanol / water (9: 1) cosolvent, and then the resulting solid is dissolved in an appropriate amount of PGMEA solvent, and then excess ethanol / water (9: 1) Drop into cosolvent to catch sediment.

The resulting solid was dried in a vacuum oven at about 50 ° C. for about 20 hours to obtain a weight average molecular weight (Mw) 3,100 polymer.

Examples 1 to 10 and Comparative Examples

Preparation of antireflective organic hard mask composition

0.9 g of the polymers prepared in Synthesis Examples 2-1 to 2-10 and Comparative Synthesis Example were respectively weighed, and 0.1 g of glycoluril compound crosslinking agent (Powderlink 1174) and pyridinium P-toluene sulfonate as a urethane curing catalyst (Pyridinium P-toluene). 1 mg of sulfonate) was dissolved in 9 g of propylene glycol monomethyl ether acetate (PGMEA) and filtered to prepare a sample solution of Synthesis Examples 2-1 to 2-10 and Comparative Synthesis Example, respectively.

Sample solutions prepared by Synthesis Examples 2-1 to 2-10 and Comparative Synthesis Examples were spin-coated onto silicon wafers, respectively, and were subjected to a temperature of 240 ° C. for 60 seconds, and Examples 1 to 10 having a form of a film having a thickness of 3000 μs. And comparative examples.

Evaluation of optical properties (refractive index, extinction coefficient) of Examples 1 to 10 and Comparative Examples

Refractive index n and extinction coefficient k for the films of Examples 1 to 10 and Comparative Examples formed by the above were obtained, respectively. The instrument used was an Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 2.

Sample Type Optical Characteristics (193nm) Optical Characteristics (248nm) Refractive index (n) Extinction coefficient (K) Refractive index (n) Extinction coefficient (K) Example 1 1.52 0.68 1.71 0.50 Example 2 1.49 0.70 1.70 0.53 Example 3 1.47 0.71 1.71 0.55 Example 4 1.51 0.68 1.71 0.54 Example 5 1.50 0.71 1.70 0.52 Example 6 1.53 0.72 1.71 0.56 Example 7 1.50 0.70 0.71 0.54 Example 8 1.51 0.71 1.73 0.55 Example 9 1.52 0.69 1.71 0.54 Preparation Example 10 1.53 0.68 1.72 0.55 Comparative example 1.45 0.69 1.96 0.36

As a result of the evaluation at the ArF (193nm) and KrF (248nm) wavelength, it was confirmed that there is a refractive index and absorbance that can be used as an antireflection film. In general, the refractive index of the material used as the semiconductor antireflection film is in the range of about 1.4 to 1.8, and the most important factor in the antireflection film is the absorption coefficient, and the higher the absorbance, the better the antireflection film. .

Lithographic Evaluation of Antireflective Organic Hardmask Compositions

Samples prepared in Synthesis Examples 2-3, 2-6, 2-8, 2-10 and Comparative Synthesis Example in Synthesis Examples 2-3, 2-6, 2-8, 2-10 and Comparative Synthesis Examples Example 3, Example 6, Example 8, Example 10, and the comparative example which corresponded to the coating film of thickness 3000K were each formed by spin-coating on this coated silicon wafer and applying a temperature of 240 degreeC for 60 second.

After coating the KrF photoresist on each of the formed coating films and applying a temperature at 110 ° C. for 60 seconds, each of them was exposed using an ASML (XT: 1400, NA 0.93) exposure equipment, followed by TMAH (tetramethyl ammonium hydroxide) Each was developed for 60 seconds with an wt% aqueous solution. Then, using a V-SEM to examine the line and space patterns of 90nm, respectively, the results are obtained as shown in Table 3 below. The exposure latitude (EL) margin according to the change in the exposure dose and the depth of focus (DoF) margin according to the distance change with the light source were considered and recorded in Table 3.

Sample type Pattern EL margin
(△ mJ / energy mJ) DoF Margin
(μm) Pattern shape Example 3 0.4 0.4 cubic Example 6 0.3 0.3 cubic Example 8 0.4 0.4 cubic Example 10 0.3 0.3 cubic Comparative example 0.1 0.1 Undercut

As a result of pattern evaluation, favorable results were confirmed in terms of profile and margin. In general, EL (expose latitude) and depth of focus (DoF) margins of 0.2 or more can be used in the litho pattern evaluation.

Evaluation of Etching Characteristics for Antireflective Organic Hard Mask Compositions

In Example 3, Example 6, Example 8, Example 10, and Comparative Example, the lower SiON anti-reflective coating (BARC) was dry-etched using PR as a mask with the CHF ₃ / CF ₄ mixed gas, respectively. Subsequently, dry etching of the present organic hard mask was performed again using a SiON antireflection film as a mask with an O ₂ / N ₂ mixed gas. After the dry etching of the silicon nitride (SiN) film with the organic hard mask as a mask using CHF ₃ / CF ₄ mixed gas, the O ₂ ashing process and the wet process of the remaining organic hard mask and organic material were performed. ) Strip process was carried out.

Immediately after the organic hardmask etching and silicon nitride etching, the cross-sections of the respective specimens were examined by V-SEM, and the results are shown in Table 4.

sample Pattern shape (after hard mask etching) Pattern shape (after SiN etching) Example 3 Vertical shape Vertical shape Example 6 Vertical shape Vertical shape Example 8 Vertical shape Vertical shape Example 10 Vertical shape Vertical shape Comparative example Slightly Boeing Boeing shape

As a result of the etch evaluation, the pattern shape after the organic hard mask etching and after the silicon nitride (SiN) etching was not bowing phenomenon in each case, and both of them were satisfactory. It was confirmed that the etching process was performed well.

While specific embodiments of the invention have been described and illustrated above, it is to be understood that the invention is not limited to the described embodiments, and that various modifications and changes can be made without departing from the spirit and scope of the invention. It is self-evident to those who have. Therefore, such modifications or variations are not to be understood individually from the technical spirit or point of view of the present invention, the modified embodiments will belong to the claims of the present invention.

Claims (9)

A polymer represented by Formula 1; And
An antireflective organic hard mask composition comprising an organic solvent:
[Formula 1]

In Chemical Formula 1,
Ar ₁ is hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amino, amidino, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted Or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C10 alkoxy group, substituted or unsubstituted C3 to C10 cycloalkyl group, substituted or unsubstituted C2 to C10 heterocycloalkyl group, substituted or Unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, or Combination of these,
X is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a combination thereof,
Y is a C1 to C20 alkylene group substituted with at least one hydroxyl group, a C6 to C30 arylene group substituted with at least one hydroxyl group, a C2 to C30 heteroaryl group substituted with at least one hydroxyl group, or a combination thereof ,
Z ₁ to Z ₃ are each Z ₁ / (Z ₁ + Z ₂ + Z ₃ ) = 0.05 to 0.45, Z ₂ / (Z ₁ + Z ₂ + Z ₃ ) = 0.5, Z ₃ / (Z ₁ + Z ₂ + Z ₃ ) = 0.05 to 0.45,
“Substituted” herein means that the hydrogen atom is substituted with a C1 to C5 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a combination thereof. The method of claim 1,
In Chemical Formula 1,
Ar ₁ is any one selected from the substituents listed in Group 1, the composition for an antireflective organic hard mask:
[Group 1]

The method of claim 1,
In Chemical Formula 1,
X is any one selected from the substituents listed in Group 2, wherein the composition for an antireflective organic hard mask:
[Group 2]

The method of claim 1,
In Chemical Formula 1,
Y is any of the substituents listed in Group 3 below, wherein the composition for an antireflective organic hardmask:
[Group 3]

The method of claim 1,
The weight average molecular weight (Mw) of the polymer is 1,000 to 30,000, antireflection organic hard mask composition. The method of claim 1,
Crosslinking agents; And
Further comprising an acid catalyst, an antireflective organic hard mask composition. The method of claim 6,
The crosslinking agent is at least one selected from the group consisting of melamine resin, amino resin, glycoluril compound and bisepoxy compound, antireflection organic hard mask composition. The method of claim 6,
The acid catalyst is p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzo At least one selected from the group consisting of intosylate, 2-nitrobenzyl tosylate and alkyl esters of organic sulfonic acids, the composition for antireflection organic hardmask. The method of claim 6,
The antireflection organic hard mask composition,
1 to 20% by weight of the polymer;
0.1 to 5% by weight of the crosslinking agent;
0.001 to 0.05% by weight of the acid catalyst; And
A composition for an antireflective organic hardmask comprising 74.95 to 98.899 weight percent organic solvent.