KR102197249B1 - reflective protective hard coating composition - Google Patents

Abstract

The present invention includes a polymer containing a polycyclic aromatic hydrocarbon represented by the following [Formula 1] or a polymer blend containing the same, and provides excellent optical properties, mechanical properties and etching selectivity to spin-on Disclosed is an anti-reflective hard coating composition that can be applied by an application technique.
[Formula 1]

Description

Reflective protective hard coating composition

The present invention relates to an anti-reflection hard coating composition, and more particularly, a polymer containing a stilbene-based polycyclic aromatic hydrocarbon having strong absorption in the ultraviolet wavelength region or a polymer mixture containing the same (blend ) It relates to an anti-reflective hard coating composition comprising a.

In recent years, as the semiconductor industry increasingly requires microscopic processes, an effective lithographic process is essential to realize such ultra-fine technology. In particular, there is an increasing demand for a new material for a hardmask process, which is very essential in the etching process.

In general, the hardmask film quality serves as an interlayer that transfers a fine pattern of a photoresist to a lower substrate layer through a selective etching process. Therefore, the hard mask layer is required to have properties such as chemical resistance, heat resistance, and etching resistance to withstand multiple etching processes. The existing hard mask film quality was made of an amorphous carbon layer (ACL) film made by chemical vapor deposition (CVD). The disadvantages of this are high cost equipment investment and particle and film quality opaque. There were many very inconvenient points to use due to photo alignment problems, etc.

Recently, instead of the chemical vapor deposition method, a spin-on hardmask method formed by a spin-on coating method has been introduced. In the spin-on coating method, an antireflection hard coating composition is formed using an organic polymer material having solubility in a solvent. In this case, the most important characteristic is that an organic polymer coating film having both etching resistance and etching resistance must be formed.

However, since the properties for solubility and etching resistance, which are two properties required for the organic hardmask layer, are in conflict with each other, an anti-reflection hard coating composition capable of satisfying all of them was required. While satisfying the characteristics of these organic hardmask materials, materials introduced into the semiconductor lithographic process have been recently introduced (Publication Patent 10-2009-0120827, Publication 10-2008-0107210, Patent WO 2013100365 A1), which is They were hardmask materials using a copolymer having an appropriate high molecular weight using hydroxypyrene.

Meanwhile, as the recent semiconductor lithographic process goes through a further refinement process, these organic hardmask materials are difficult to perform sufficiently as a mask due to the lack of etching selectivity in the etching process compared to conventional inorganic hardmask materials. Came. Therefore, there is an urgent need to introduce an organic hardmask material more optimized for the etching process.

Patent Publication 10-2009-0120827 Patent Publication 10-2008-0107210 Patent WO 2013100365 A1

The present invention provides a lithographic technology using a composition having excellent solubility in a solvent, high etching selectivity, sufficient resistance to multi etching, and minimizing reflectivity between the resist and the back layer. It is an object to provide an anti-reflective hard coating composition that can be used to perform.

Meanwhile, the technical problems to be achieved in the present invention are not limited to the technical problems mentioned above, and other technical problems that are not mentioned are clearly to those of ordinary skill in the technical field to which the present invention belongs from the following description. It will be understandable.

The anti-reflection hard coating composition according to an embodiment of the present invention includes a polymer containing a polycyclic aromatic hydrocarbon represented by the following [Chemical Formula 1] or a polymer blend containing the same.

[Formula 1]

(Here, m and n have a range of 1=m≤=20, 0=n≤=20, and 1=m+n≤=20, respectively.)

In [Chemical Formula 1], A may be one of stilbene derivatives represented by the following [Chemical Formula 2].

[Formula 2]

In [Chemical Formula 1], B may be one co-monomer selected from the following [Chemical Formula 3].

[Chemical Formula 3]

In [Chemical Formula 1], C may be one selected from aliphatic or aromatic aldehyde, acetal, ketal, di-alkoxy, and divinyl aromatic. .

Organic solvent; It may further include.

Crosslinking agent; And an acid catalyst; It may further include.

1 to 30% by weight of a polycyclic aromatic hydrocarbon polymer represented by [Chemical Formula 1] or a polymer blend comprising the same; 0.1 to 5% by weight of a crosslinking agent; 0.001 to 0.05% by weight of acid catalyst; And an organic solvent as the remaining component, and may be made of 100% by weight in total.

The crosslinking agent is a melamine-based crosslinking agent, a urea-based crosslinking agent, an ethyleneurea-based crosslinking agent, a propylene urea-based crosslinking agent, a glycoluril-based crosslinking agent, a hydroxyl group, a hydroxylalkyl group, or an aliphatic cyclic hydrocarbon having a combination thereof, or an aliphatic cyclic hydrocarbon oxygen. It may be any one selected from the group consisting of containing derivatives, glycoluril compounds, etherified amino resins, and combinations thereof.

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

The organic solvent is propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; Glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); Carboxylate, ethyl acetate, n-butyl acetate and amyl acetate; Carboxylate, diethyloxylate and diethylmalonate of dibasic acids; Dicarboxylate of glycol, ethylene glycol diacetate and propylene glycol diacetate; And hydroxycarboxylate, methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxy propionate; Ketone esters, methylpyruvate or ethyl pyruvate; Alkoxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; Ketone derivatives, methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; Ketone ether derivatives, diacetone alcohol methyl ether; Ketone alcohol derivatives, acetol or diacetone alcohol; Ketal or acetal, 1, 3-dioxalane and diethoxypropane; Lactone, butyrolactone and gamma valerolactone; Amide derivatives, dimethylacetamide or dimethylformamide, anisole; And it may be any one selected from the group consisting of a mixture thereof.

According to an embodiment of the present invention, it is possible to minimize the reflectivity between the resist and the back layer by having a useful range of refractive index and absorption as an antireflection film in the deep UV region such as ArF (193 nm) and KrF (248 nm) during film formation. have.

In addition, according to an embodiment of the present invention, it is made of Stilbenederivatives, and when forming a thin film due to a high packing density, it has a property of excellent etching resistance while increasing the film density. The ratio is high and the resistance to multiple etchings is sufficient, so that an excellent pattern evaluation result can be obtained.

On the other hand, the effects obtainable in the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those of ordinary skill in the art from the following description. I will be able to.

Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings. The embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. This embodiment is provided to more completely describe the present invention to those with average knowledge in the art. Therefore, the shape of the element in the drawings has been exaggerated to emphasize a clearer description.

The configuration of the invention for clarifying the solution to the problem to be solved by the present invention will be described in detail with reference to the accompanying drawings based on a preferred embodiment of the present invention, but the same in assigning reference numerals to the components of the drawings For the components, even if they are on different drawings, the same reference numerals are given, and it should be noted in advance that components of other drawings may be referred to when necessary when describing the drawings.

The antireflective hard coating composition according to an embodiment of the present invention may include a polymer containing a polycyclic aromatic hydrocarbon represented by the following [Chemical Formula 1] or a polymer blend containing the same.

[Formula 1]

(Here, m and n each have a range of 1=m≤=20, 0=n≤=20, 1=m+n≤=20, and A is a stilbene derivative represented by the following [Formula 2] ( stilbene derivatives), and B, which is a co-monomer, is any one selected from the following [Chemical Formula 3], and C is an aliphatic or aromatic aldehyde, acetal, or ketal ( ketal), di-alkoxy, and divinyl aromatic, and forms a methylene bridge as shown in [Formula 4] below.)

[Formula 2]

(Here, R1 and R4 in Formula 2 are hydrogen, hydroxyl, alkoxy having 1 to 4 carbon atoms, alkyl group having 1 to 4 carbon atoms, and dialkoxyalkyl group having 1 to 4 carbon atoms ( dialkoxyalkyl) and one selected from a carboxylic acid alkyl ester having 1 to 4 carbon atoms, and R2 and R3 are selected from hydrogen, an alkyl group having 1 to 2 carbon atoms, and a benzoxazolyl group. And R5 and R6 are one selected from an alkyl group having 1 to 2 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, and R7, R8, R9 and R10 are hydrogen and an alkyl group having 1 to 2 carbon atoms It is one selected from (alkyl).

[Chemical Formula 3]

(Here, R1 in Formula 3 is one selected from hydrogen, hydroxyl, or an alkyl group having 1 to 4 carbon atoms, and an alkoxy group.)

In Formula 1, C forming a methylene bridge and polymerizing monomers is an aliphatic or aromatic aldehyde, acetal, ketal, di-alkoxy, or It is divinyl aromatic, and the number of aliphatic carbons is preferably within 1 to 4 in order to reduce oxidation during sintering after spin-on coating.

[Formula 4]

That is, the antireflection hard coating composition of the embodiment of the present invention includes a polymer containing a polycyclic aromatic hydrocarbon represented by [Chemical Formula 1] or a polymer blend containing the same, and is strong in a short wavelength region. Since it contains an aromatic hydrocarbon having absorption, it can be usefully used as a component of an antireflective hard coating composition having antireflection properties.

On the other hand, the anti-reflection hard coating composition of the embodiment of the present invention (a) a polymer containing a polycyclic aromatic hydrocarbon (polycyclic aromatic hydrocarbon) represented by [Formula 1] or a copolymer comprising the same; And (b) an organic solvent.

In the anti-reflection hard coating composition of the present invention, the polymer containing a polycyclic aromatic hydrocarbon represented by [Chemical Formula 1] or the aromatic hydrocarbon of the copolymer containing the same is present in the skeleton of the polymer. Preferably, the aromatic hydrocarbon (aromatic hydrocarbon) absorbs ultraviolet rays of a short wavelength during the lithographic process, so that the antireflection hard coating composition of the present invention can minimize the reflectivity between the rear layers without a separate antireflection coating (ARC).

In addition, it is preferable that a polymer containing a polycyclic aromatic hydrocarbon represented by [Formula 1] or an aromatic hydrocarbon of a copolymer containing the same has at least one hydroxyl or alkoxy group in the molecule. .

Hydroxyl and alkoxy groups not only increase the selectivity to react to the ortho or para position during a methylene bridge reaction to an aromatic hydrocarbon, but also a high temperature bake ), it is possible to increase the etching resistance by increasing the density of the crosslinking agent by promoting the self-curing reaction or the curing reaction with the added crosslinking agent.

In [Formula 1] m/(m+n) has a value in the range of 0.05 to 1.0, and the number average molecular weight (Mn, number average molar mass) of the entire copolymer is 500 to 5,000 Daltons, preferably Is preferably 1, 000 to 3, 500 Daltons.

On the other hand, the polycyclic aromatic hydrocarbon group (alicyclic group) may be monocyclic or polycyclic. Specifically, a group having a monocyclo, bicyclo, tricyclo, tetracyclo structure and the like having 5 or more carbon atoms can be illustrated.

The number of carbon atoms is preferably 6 to 30, and particularly preferably 7 to 25 carbon atoms. Here, the number of carbon atoms is the number of carbon atoms constituting the ring. These alicyclic groups may have a substituent other than a hydroxyl group.

Preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decarinic residue, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. , A cyclodecanyl group and a cyclododecanyl group. More preferably, they are an adamantyl group, a decarinic residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

Examples of the substituents other than the hydroxyl group that the alicyclic group may have include an alkyl group, a substituted alkyl group, a halogen atom, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group.

Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group.

Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The hydroxyl group possessed by the alicyclic group may be substituted with either the alicyclic ring itself or a substituent portion of the alicyclic ring. The number of hydroxyl groups that the alicyclic group has is preferably 1 or 2, more preferably 2.

On the other hand, the organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in a polymer containing a polycyclic aromatic hydrocarbon, for example, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone, or Ethyl lactate and the like.

For example, these organic solvents are glycol ether derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene Glycol n-propyl ether, or diethylene glycoldimethyl ether; Glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); Carboxylates such as ethyl acetate, n-butylacetate and amyl acetate; Carboxylates of dibasic acids such as diethyloxylate and diethylmalonate; Dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; And hydroxycarboxylates such as methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxy propionate; Ketone esters such as methylpyruvate or ethyl pyruvate; Alkoxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; Ketone derivatives such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; Ketone ether derivatives such as diacetone alcohol methyl ether; Ketone alcohol derivatives such as acetol or diacetone alcohol; Ketal or acetal such as 1, 3-dioxalane and diethoxypropane; Lactones such as butyrolactone and gamma valerolactone; Amide derivatives such as dimethylacetamide or dimethylformamide, anisole; And mixtures thereof.

On the other hand, in order to make the anti-reflection hard coating composition according to an embodiment of the present invention, (a) a polymer containing a polycyclic aromatic hydrocarbon or a polymer blend containing the same (b) 100 weight of an organic solvent It is preferable to use 1 to 50 parts by weight based on parts.

Here, when (a) a polymer containing a polycyclic aromatic hydrocarbon or a copolymer containing the same (b) less than 1 part by weight or more than 50 parts by weight based on 100 parts by weight of the organic solvent, the desired coating thickness There is a problem in that it becomes less than or exceeds so that it is difficult to match the correct coating thickness.

In addition, the anti-reflection hard coating composition according to an embodiment of the present invention may additionally include (c) a crosslinking agent and (d) an acid catalyst.

(C) The crosslinking agent used in the antireflection hard coating composition of the present invention is preferably capable of crosslinking the repeating units of the polymer by heating in a reaction catalyzed by the generated acid, and (d) the acid catalyst is thermally activated. It is preferably an acid catalyst to be used.

For example, examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; Organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid and oxalic acid; Unsaturated organic acids, such as methacrylic acid, acrylic acid, and itaconic acid, may be included.

Preferred examples of these are organic acids and unsaturated organic acids.

Meanwhile, a base catalyst may be added as a catalyst to accelerate the reaction.

Examples of the base include primary, secondary or tertiary aliphatic amines such as aqueous ammonia, diethylamine, triethylamine, dibutylamine, and cyclohexylamine, aromatic amines such as pyridine, sodium hydroxide, potassium hydroxide, and tetramethyl And quaternary ammonium hydroxides such as ammonium hydroxide and tetrabutylammonium hydroxide.

Among these, preferred examples of the base may be tertiary amines or quaternary ammonium hydroxides.

On the other hand, it is also preferable to add a dehydrating agent in order to accelerate the reaction.

As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Among them, organic compounds are preferred, and ortho esters such as methyl orthoformate and ethyl orthoformate are more preferred. Here, (c) the crosslinking agent is an etherified amino resin, such as a methylated or butylated melamine resin (specific examples, for example, N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin) and methylated or butyl Urea Resin (specific examples, Cymel U-65 Resin or UFR 80 Resin), glycoluril compounds (specific examples, Powderlink 1174), or bisepoxy compounds (specific examples include 2, 6-bis ( Hydroxymethyl)-p-cresol compound) and the like.

However, (c) the crosslinking agent is preferably a crosslinking agent capable of reacting with a hydroxyl group of a polymer containing a polycyclic aromatic hydrocarbon in a manner that can be catalytically functionalized by the produced acid, and in the present invention Of course, this is not specifically limited.

In addition, (d) an organic acid such as p-toluenesulfonic acid monohydrate or triflic acid may be used as the acid catalyst, and TAG (Thermal Acid Generator), which aims at storage stability. System compounds can be used as catalysts.

Here, TAG is an acid-generating compound that is to release an acid during heat treatment, for example, pyridinium P-toluene sulfonate, 2, 4, 4, 6-tetrabromo-2, 5 -Cyclohexadienone (2, 4, 4, 6-tetrabromo-2, 5-cyclohexadienone), benzoin tosylate, 2-nitrobenzyl tosylate and sulfonic acid alkyl esters (sulfonic acid alkyl ester), and the like.

On the other hand, the crosslinking agent is a melamine-based crosslinking agent, a urea-based crosslinking agent, an ethyleneurea-based crosslinking agent, a propylene urea-based crosslinking agent, a glycoluril-based crosslinking agent, a hydroxyl group, a hydroxylalkyl group, or an alicyclic hydrocarbon having a combination thereof, or an alicyclic hydrocarbon. It may be an oxygen-containing derivative, a glycoluril compound, an etherified amino resin, a combination thereof, and the like.

In addition, specific examples of materials that can be used as crosslinking agents include melamine, acetoguanamine, benzoguanamine, urea, ethylene urea, or glycoluril with formaldehyde, glycoluril with a combination of formaldehyde and lower alcohol, hexamethoxy. Methylmelamine, bismethoxymethylurea, bismethoxymethylbismethoxyethyleneurea, tetramethoxymethylglycoluril, and tetrabutoxymethylglycoluril, mono-, di-, tri-, or tetra-hydroxymethylated glycol Luryl, mono-, di-, tri-, and/or tetra-methoxymethylated glycoluril, mono-, di-, tri-, and/or tetra-ethoxymethylated glycoluril, mono-, di-, tri- , And/or tetra-propoxymethylated glycoluril, and mono-, di-, tri-, and/or tetra-butoxymethylated glycoluril, 2, 3-dihydroxy-5-hydroxymethylnovonane, 2 -Hydroi-5, 6-bis (hydroxymethyl) nobonane, cyclohexanedimethanol, 3, 4, 8 (or 9)-trihydroxytricyclodecane, 2-methyl-2-adamantanol, 1, 4-dioxane-2, 3-diol and 1, 3, 5-trihydroxycyclohexane, tetramethoxymethylglycoluryl, methylpropyltetramethoxymethylglycoluryl, and methylphenyltetramethoxymethylglycoluril, 2, 6-bis(hydroxymethyl)p-cresol, N-methoxymethyl- or N-butoxymethyl-melamine.

Additionally, formaldehyde, or formaldehyde and lower alcohols and amino group-containing compounds such as melamine, acetoguanamine, benzoguanamine, urea, ethylene urea and glycoluril are reacted, and the hydrogen atom of the amino group is hydroxy Compounds obtained by substituting a methyl group or a lower alkoxymethyl group, such as hexamethoxymethylmelamine, bismethoxymethylurea, bismethoxymethylbismethoxyethyleneurea, tetramethoxymethylglycoluril and tetrabutoxymethylglycoluryl , 3-chloro-2-hydroxypropyl methacrylate and a copolymer of methacrylic acid, 3-chloro-2-hydroxypropyl methacrylate and a copolymer of cyclohexyl methacrylate and methacrylic acid, 3-chloro -2-hydroxypropyl methacrylate and a copolymer of benzyl methacrylate and methacrylic acid, bisphenol A-di(3-chloro-2-hydroxypropyl) ether, poly(3-chloro-) of phenol novolak resin 2-hydroxypropyl) ether, pentaerythritol tetra (3-chloro-2-hydroxypropyl) ether, trimethylolmethane tri (3-chloro-2-hydroxypropyl) ether phenol, bisphenol A-di (3 -Acetoxy-2-hydroxypropyl) ether, poly(3-acetoxy-2-hydroxypropyl) of phenol novolak resin, pentaerythritol tetra(3-acetoxy-2-hydroxypropyl) ether, Pentaerythritol poly(3-chloroacetoxy-2-hydroxypropyl) ether, trimethylolmethane tri(3-acetoxy-2-hydroxypropyl) ether, or a combination thereof.

On the other hand, when the final anti-reflective hard coating composition further comprises (c) a crosslinking agent and (d) an acid catalyst, the anti-reflection hard coating composition according to an embodiment of the present invention has strong absorption properties in the ultraviolet region ( a) 1 to 30 parts by weight of a copolymer consisting of Stilbene derivatives, more preferably 3 to 15 parts by weight, (c) 0.1 to 5 parts by weight of a crosslinking agent, more preferably 0.1 to 3 parts by weight Includes, (d) 0.001 to 0.05 parts by weight of an acid catalyst, more preferably 0.001 to 0.03 parts by weight, and the remaining components may consist of a total of 100 parts by weight using (b) an organic solvent, preferably an organic solvent 62 It may contain to 98 parts by weight.

Here, (a) when the polymer containing a polycyclic aromatic hydrocarbon is less than 1 part by weight or exceeds 30 parts by weight, it becomes less than or exceeds the desired coating thickness, making it difficult to match the exact coating thickness.

And (c) when the crosslinking agent is less than 0.1 parts by weight, the crosslinking agent properties may not appear, and when the crosslinking agent exceeds 5 parts by weight, there is a problem that the optical properties of the coating film may be changed due to excessive injection.

In addition, (d) if the amount of the acid catalyst is less than 0.001 parts by weight, the crosslinking agent characteristics may not be exhibited well, and if it exceeds 0.05 parts by weight, the storage stability may be adversely affected due to an increase in acidity due to excessive injection.

Hereinafter, an anti-reflection hard coating composition according to an embodiment of the present invention manufactured through various manufacturing examples will be described.

<Example 1>

Diethylstilbestrol 13.4 g (50 mmol) and 1, 4-bis (methoxymethyl) benzene (1, 4-bis (methoxymethyl) benzene) 16.6 g (100 mmol) in a 250 ml 4-neck round flask, and 7.2 g (50 mmol) of 1-naphthol was dissolved in 87 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in nitrogen atmosphere, and then 1.2 g (4 mole%) of triflic acid Add

Thereafter, the reaction solution was reacted at a reaction temperature of 140° C. for 5 hours while refluxing, and then cooled to room temperature.

Thereafter, 40 ml of cyclopentylmethylether was added to the reaction solution, washed twice with 40 ml of ion-exchanged water (DIW), and then added dropwise to 800 ml of methanol to catch the precipitate, and the precipitate was filtered through nuche type. After filtering with a Nutsche filter dryer, it is washed twice with methanol.

Thereafter, the filtered and washed precipitate was dried under vacuum at 85° C. for 12 hours to obtain a copolymer of [Formula 5] consisting of a stilbene derivative having a number average molecular weight (Mn) of 1,750. I can.

[Formula 5]

<Example 2>

4'-hydroxy-3, 5-dimethoxy stilbene (4'-hydroxy-3, 5-dimethoxy stilbene) 12.8g (50mmol) and 1, 4-bis (methoxymethyl) in a 250ml 4-neck round flask ) Benzene (1, 4-bis (methoxymethyl)benzene) 16.6g (100mmol), 1-naphthol (1-naphthol) 7.2g (50mmol) at 60 degrees gamma butyrolactone (GBL; γ-Butyrolactone) 86g After dissolving in a nitrogen atmosphere, 1.2 g (4 mole%) of triflic acid is added.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 6] consisting of a stilbene derivative having a number average molar mass (Mn) of 1,700 You can get coalescence.

[Formula 6]

<Example 3>

In a 250ml 4-neck round flask, 4-diphenylamino stilbene 17.35g (50mmol) and 1, 4-bis (methoxymethyl)benzene (1, 4-bis (methoxymethyl)benzene) 16.6g (100 mmol), and 7.2 g (50 mmol) of 1-naphthol were dissolved in 96 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in a nitrogen atmosphere, and then triflic acid 1.2 Add g (4 mole%).

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 7] consisting of a stilbene derivative having a number average molar mass (Mn) of 2,000 You can get coalescence.

[Formula 7]

<Example 4>

In a 250 ml 4-neck round flask, 22.1 g (50 mmol) of bis-5-methyl-benzoxazolyl stilbene and 1, 4-bis (methoxymethyl) benzene (1, 4-bis) (methoxymethyl)benzene) 16.6g (100mmol) and 1-naphthol 7.2g (50mmol) were dissolved in 107 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in a nitrogen atmosphere. Add 1.2 g (4 mole%) of triflic acid.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 8] consisting of a stilbene derivative having a number average molar mass (Mn) of 2,300 You can get coalescence.

[Formula 8]

<Example 5>

In a 250 ml 4-neck round flask, 22.1 g (50 mmol) of bis-5-methyl-benzoxazolyl stilbene and 1, 4-bis (methoxymethyl) benzene (1, 4-bis) (methoxymethyl)benzene) 16.6g (100mmol) and paracresol (p-cresol) 5.4g (50mmol) dissolved in 103g of gamma butyrolactone (GBL; γ-Butyrolactone) at 60 degrees in nitrogen atmosphere Add 1.2 g (4 mole%) of triflic acid.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 9] consisting of a stilbene derivative having a number average molar mass (Mn) of 2,200 You can get coalescence.

[Formula 9]

<Example 6>

In a 250 ml 4-neck round flask, 22.1 g (50 mmol) of bis-5-methyl-benzoxazolyl stilbene and 1, 4-bis (methoxymethyl) benzene (1, 4-bis) (methoxymethyl)benzene) 16.6g (100mmol), 1-hydroxypyrene (1-hydroxypyrene) 10.9g (50mmol) dissolved in 115g of gamma butyrolactone (GBL; γ-Butyrolactone) at 60 degrees in nitrogen atmosphere After that, 1.2 g (4 mole%) of triflic acid is added.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the aerial of [Formula 10] consisting of a stilbene derivative having a number average molar mass (Mn) of 2,500 You can get coalescence.

[Formula 10]

<Example 7>

250ml 4-neck round flask Yebisu-5-methylbenzoxazolyl stilbene 22.1g (50mmol) and 1, 4-bis (methoxymethyl) benzene (1, 4-bis ( methoxymethyl)benzene) 16.6 g (100 mmol), and 9, 9'-bishydroxyphenyl fluorene (9, 9'-bishydroxyphenyl fluorene) 17.5 g (50 mmol) at a temperature of 60 degrees gamma butyrolactone (GBL; γ- After dissolving 131 g of butyrolactone) in a nitrogen atmosphere, 1.2 g (4 mole%) of triflic acid is added.

Thereafter, a copolymer of [Formula 11] consisting of a stilbenederivative having a number average molecular weight (Mn) of 2,700 by synthesis, filtration, washing and drying in the same manner as in <Example 1> Can be obtained.

[Formula 11]

<Example 8>

In a 250 ml 4-neck round flask, bis-5-methyl-benzoxazolyl stilbene 44.2 g (100 mmol) and 1, 4-bis (methoxymethyl) benzene (1, 4-bis) Dissolve 16.6 g (100 mmol) of (methoxymethyl)benzene) in 142 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in a nitrogen atmosphere, and then add 1.2 g (4 mole%) of triflic acid. .

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 12] consisting of a stilbene derivative having a number average molar mass (Mn) of 3,200 You can get coalescence.

[Formula 12]

<Example 9>

4, 4'-bis (5-methyl-2-benzoxazolyl) stilbene (4, 4'-bis (5-methyl-2-benzoxazolyl) stilbene) 44.2 g (100 mmol) in a 250 ml 4-neck round flask After dissolving 16.6 g (100 mmol) of 1, 4-bis(methoxymethyl)benzene) in 142 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in a nitrogen atmosphere, Add 1.2 g (4 mole%) of triflic acid.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the aerial of [Formula 13] consisting of a stilbene derivative having a number average molecular weight (Mn) of 3,200 You can get coalescence.

[Formula 13]

<Comparative Example 1>

In a 250-mL 4-neck round flask, add 35 g (100 mmol) of 9, 9'-bishydroxyphenyl fluorene and 10.6 g (100 mmol) of benzaldehyde at a temperature of 60 degrees gamma butyrolactone. After dissolving 106 g of (GBL; γ-Butyrolactone) in a nitrogen atmosphere, 1.2 g (4 mole%) of triflic acid is added.

Thereafter, synthesis, filtration, washing, and drying in the same manner as in <Example 1> were carried out to obtain a copolymer of [Formula 14] consisting of a fluorene derivative having a number average molar mass (Mn) of 2,500. You can get coalescence.

[Formula 14]

<Comparative Example 2>

In a 250ml 4-neck round flask, 17.5g (50mmol) of 9, 9'-bishydroxyphenyl fluorene and 1,4-bismethoxymethylbenzene (1,4-bis(methoxymethyl) )benzene) 16.6 g (100 mmol), and paracresol (p-cresol) 5.4 g (50 mmol) dissolved in 106 g of gamma butyrolactone (GBL; γ-Butyrolactone) at a temperature of 60 degrees in nitrogen atmosphere, and then triflic acid ( Triflic acid) 1.2g (4mole%) is added.

Thereafter, by synthesis, filtration, washing and drying in the same manner as in <Example 1>, the air of [Formula 15] consisting of a fluorene derivative having a number average molar mass (Mn) of 2,000 You can get coalescence.

[Formula 15]

<Comparative verification of Examples 1 to 9 and Comparative Examples 1 and 2>

Preparation of anti-reflective hard coating composition

The polymers prepared in Examples 1 to 9 and Comparative Examples 1 and 2 were weighed by 0.9 g each, and 0.1 g of glycoluril cross-linking agent (Powderlink 1174) and pyridinium P-toluene sulfonate (Pyridinium P-toluene sulfonate) 　 1 mg were added to propylene glycol monomethyl. After dissolving in 9 g of ether acetate (PGMEA) and filtering to prepare the sample solutions of Examples 1 to 9 and Comparative Examples 1 and 2, respectively, the sample solutions prepared by Examples 1 to 9 and Comparative Examples 1 and 2 were each The silicon wafer was spin coated and fired at 240° C. for 60 seconds to form a film having a thickness of 3000 Å.

At this time, the refractive index n and the extinction coefficient k of the formed 　 films were obtained, respectively.

Here, the used device was an Ellipsometer (J. A. Woollam), and the measurement results for this are shown in 　[Table 1].

Sample type Optical characteristics (193nm) Optical characteristics (248nm) Refractive index (n) Extinction coefficient (k) Refractive index (n) Extinction coefficient (k) Example 1 1.51 0.68 1.70 0.53 Example 2 1.50 0.70 1.71 0.53 Example 3 1.49 0.71 1.70 0.52 Example 4 1.52 0.69 1.73 0.53 Example 5 1.54 0.70 1.72 0.54 Example 6 1.53 0.71 1.72 0.54 Example 7 1.52 0.69 1.73 0.55 Example 8 1.52 0.70 1.73 0.53 Example 9 1.51 0.68 1.70 0.52 Comparative Example 1 1.48 0.68 1.95 0.35 Comparative Example 2 1.49 0.66 1.75 0.33

As a result of the evaluation, it can be confirmed that the antireflection hard coating composition prepared according to the present invention has excellent refractive index and absorption that can be used as an antireflection film at ArF (193 nm) and KrF (248 nm) wavelengths. The refractive index range of the material to be used is about 1.4 to 1.8. Here, the important thing is the extinction coefficient, which is preferable as the absorbance is higher, and if the k value is usually 0.3 or more, there is no problem in using it as an antireflection film.

That is, it can be seen that the antireflection hard coating composition according to the embodiments of the present invention has a refractive index of about 1.4 to 1.8 and an extinction coefficient of 0.5 or more depending on the wavelength, and thus can be used as an antireflection film.

Lithographic evaluation of anti-reflective hard coating composition

The sample solutions prepared in Examples 2, 4, 6, 8 and Comparative Examples were spin-coated on a silicon wafer coated with aluminum, respectively, and fired at 240°C for 60 seconds to form a 3000Å-thick coating film, and then for KrF on each of the formed coating films. The photoresist was coated and baked at 110° C. for 60 seconds, and exposure was performed using an exposure equipment manufactured by ASML (XT:1400, NA 0.93), and then developed with a 2.38 wt% aqueous solution of TMAH (tetramethyl ammonium hydroxide) for 60 seconds.

Thereafter, as a result of examining each of the 90 nm line and space patterns using V-SEM, the results shown in Table 2 below were obtained.

Sample type Pattern characteristics EL margin
(△mJ/energy mJ) DoF margin
(㎛) Pattern shape Example 1 0.3 0.3 cubic Example 2 0.4 0.4 cubic Example 3 0.2 0.3 undercut Example 4 0.3 0.3 cubic Example 5 0.3 0.3 cubic Example 6 0.4 0.4 cubic Example 7 0.2 0.2 undercut Example 8 0.3 0.3 cubic Example 9 0.3 0.3 cubic Comparative Example 1 0.1 0.2 undercut Comparative Example 2 0.1 0.2 undercut

According to the results of examining the EL (expose latitude) margin according to the change in exposure amount and the DoF (depth of focus) margin according to the distance change from the light source, the anti-reflection hard coating composition prepared according to the present invention It was found that the silver profile and margin were satisfactory and satisfies the EL margin and DoF margin required in the evaluation of the litho pattern.

Evaluation of etching properties for antireflective hard coating compositions

In Examples 2, 4, 6, and Comparative Examples, each patterned sample was dry etched with a CHF ₃ /CF ₄ mixed gas and PR as a mask, followed by dry etching of the lower SiON antireflection film (BARC), followed by O ₂ /N ₂ Dry etching of this hard mask was performed again using the SiON antireflection film as a mask as a mixed gas.

Afterwards, dry etching the silicon nitride (SiN) film quality using the CHF ₃ /CF ₄ mixed gas as a mask, and then O ₂ ashing and wet strip for the remaining hard mask and organic matter. The process proceeded.

Immediately after hard mask etching and silicon nitride etching, the cross-sections of each specimen were examined with V-SEM, and the results are shown in [Table 3].

Sample Pattern shape (after hard mask etching) Pattern shape (after SiN etching) Example 1 Vertical shape Vertical shape Example 2 Vertical shape Vertical shape Example 3 Vertical shape A little boeing Example 4 Vertical shape Vertical shape Example 5 Vertical shape Vertical shape Example 6 Vertical shape Vertical shape Example 7 Vertical shape A little boeing Example 8 Vertical shape Vertical shape Example 9 Vertical shape Vertical shape Comparative Example 1 A little boeing Boeing Comparative Example 2 A little boeing Boeing

As a result of the etching evaluation, the pattern shape of the anti-reflection hard coating composition prepared according to the present invention after hard mask etching and silicon nitride etching in each case was good without bowing, so the resistance by the etching process was sufficient. It can be seen that the etching process of the silicon nitride film was satisfactorily performed.

The detailed description above is illustrative of the present invention. In addition, the above description shows and describes preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications and environments. That is, changes or modifications may be made within the scope of the concept of the invention disclosed in the present specification, the scope equivalent to the disclosed contents, and/or the skill or knowledge of the art. The above-described embodiments describe the best state for implementing the technical idea of the present invention, and various changes required in the specific application fields and uses of the present invention are possible. Therefore, the detailed description of the invention is not intended to limit the invention to the disclosed embodiment. In addition, the appended claims should be construed as including other embodiments.

Claims (10)

Including a polymer containing a polycyclic aromatic hydrocarbon (polycyclic aromatic hydrocarbon) represented by the following [Formula 1] or a polymer mixture (blend) containing the same,
In the following [Formula 1],
C is an antireflection hard coating composition selected from aliphatic or aromatic aldehyde, acetal, ketal, di-alkoxy and divinyl aromatic.
[Formula 1]

(Where, A is stilbene derivatives, B is a co-monomer, C is a methylene bridge,
m and n have a range of 1=m≤20, 0=n≤=20, and 1=m+n≤=20, respectively.)
The method of claim 1,
In the above [Formula 1],
The A is one of stilbene derivatives represented by the following [Chemical Formula 2] anti-reflection hard coating composition.
[Formula 2]

(Here, R1 and R4 in Formula 2 are hydrogen, hydroxyl, alkoxy having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, alkyl carboxylic acid having 1 to 4 carbon atoms ( carboxylic acid alkyl ester), R2 and R3 are one selected from hydrogen, an alkyl group having 1 to 2 carbon atoms, and a benzoxazolyl group, and R5 and R6 are an alkyl group having 1 to 2 carbon atoms (alkyl) and one selected from an alkoxy group having 1 to 4 carbon atoms, and R7, R8, R9, and R10 are selected from hydrogen and an alkyl group having 1 to 2 carbon atoms)
The method of claim 2,
In the above [Formula 1],
The B is one comonomer (co-monomer) selected from the following [Formula 3] Anti-reflection hard coating composition.
[Chemical Formula 3]

(Here, R1 in Formula 3 is one selected from hydrogen, hydroxyl, or an alkyl group having 1 to 4 carbon atoms, and an alkoxy group.)
delete The method of claim 1,
Organic solvent; Anti-reflection hard coating composition further comprising a.
The method of claim 5,
Crosslinking agent; And an acid catalyst; Anti-reflection hard coating composition further comprising a.
The method of claim 6,
1 to 30% by weight of a polycyclic aromatic hydrocarbon polymer represented by [Chemical Formula 1] or a polymer blend containing the same;
0.1-5% by weight of a crosslinking agent;
0.001-0.05% by weight of acid catalyst; And
An antireflection hard coating composition consisting of 100% by weight and using an organic solvent as the remaining component.
The method of claim 7,
The crosslinking agent is a melamine-based crosslinking agent, a urea-based crosslinking agent, an ethyleneurea-based crosslinking agent, a propylene urea-based crosslinking agent, a glycoluril-based crosslinking agent, a hydroxyl group, a hydroxylalkyl group, or an aliphatic cyclic hydrocarbon having a combination thereof, or an aliphatic cyclic hydrocarbon Antireflection hard coating composition which is any one selected from the group consisting of containing derivatives, glycoluril compounds, etherified amino resins, and combinations thereof.
The method of claim 7,
The acid catalyst is p-toluenesulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2, 4, 4, 6-tetrabromocyclohexadienone, benzo Intosylate, 2-nitrobenzyl tosylate, alkyl esters of organic sulfonic acid and triplic acid, any one selected from the group consisting of antireflection hard coating composition.
The method of claim 7,
The organic solvent is
Propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone or ethyl lactate, glycol ether derivatives, ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, dipropylene glycoldimethyl ether, propylene glycol n-propyl ether, or diethylene glycoldimethyl ether; Glycol ether ester derivatives, ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); Carboxylate, ethyl acetate, n-butyl acetate and amyl acetate; Carboxylate, diethyloxylate and diethylmalonate of dibasic acids; Dicarboxylate of glycol, ethylene glycol diacetate and propylene glycol diacetate; And hydroxycarboxylate, methyl lactate, ethyl lactate, ethyl glycolate, and ethyl-3-hydroxy propionate; Ketone esters, methylpyruvate or ethyl pyruvate; Alkoxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; Ketone derivatives, methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; Ketone ether derivatives, diacetone alcohol methyl ether; Ketone alcohol derivatives, acetol or diacetone alcohol; Ketal or acetal, 1, 3-dioxalane and diethoxypropane; Lactone, butyrolactone and gamma valerolactone; Amide derivatives, dimethylacetamide or dimethylformamide, anisole; And any one selected from the group consisting of a mixture of these anti-reflection hard coating composition.