KR101174086B1 - Polymer, polymer composition, under-layer composition of resist, and patterning method of materials using the same - Google Patents

Abstract

The present invention relates to a polymer, a polymer composition, a resist underlayer film composition including the same, and a patterning method of a material using the same. The polymer according to the present invention has a repeating unit represented by the following Chemical Formula 1.

[Formula 1]

(In Formula 1, the definitions of Ar ₁ , Ar ₂ and Z ₁ to Z ₄ are as described in the specification.)

The polymer, the polymer composition, and the resist underlayer film composition according to the present invention have a refractive index and absorbance within a suitable range as an antireflection film in a DUV (deep UV) wavelength region such as ArF (193 nm) and KrF (248 nm) when forming a film. Reflectivity between the resist and the underlying layer can be minimized, and the lithographic technique has a high etching selectivity and sufficient resistance to multiple etching, thereby providing a lithographic structure excellent in pattern shape and margin.

Lithographic, antireflective, hard mask, aromatic rings

Description

Polymer, polymer composition, resist underlayer film composition comprising same and patterning method of material using same {POLYMER, POLYMER COMPOSITION, UNDER-LAYER COMPOSITION OF RESIST, AND PATTERNING METHOD OF MATERIALS USING THE SAME}

The present invention relates to a polymer, a polymer composition, a resist underlayer film composition comprising the same, and a patterning method of a material using the same. More particularly, the present invention provides very excellent optical properties, mechanical properties, and etching selectivity properties, and simultaneously spin- The present invention relates to a polymer, a polymer composition, a resist underlayer film composition including the same, and a method of patterning a material using the on-coating technique, which are useful for a shorter wavelength lithographic process and minimize residual acid retention. .

In the microelectronics industry as well as in other industries, including the fabrication of microscopic structures (eg, micromachines, magnetoresist heads, etc.), there is a continuing need to reduce the size of structural features. In the microelectronics industry, there is a desire to reduce the size of microelectronic devices, thereby providing a larger amount of circuitry for a given chip size.

Effective lithographic techniques are essential to achieving a reduction in shape size. Lithographic influences the fabrication of microscopic structures not only in terms of directly imaging a pattern on a given substrate, but also in the manufacture of masks typically used for such imaging.

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

Most of the lithographic processes increase the resolution by using an anti-reflective coating (ARC) to minimize the reflectivity between the imaging layer, such as the photosensitive resist material layer and the underlying layer. However, many imaging layers may also be consumed during the etching of the ARC after patterning, requiring further patterning during subsequent etching steps.

In other words, for some lithographic imaging processes, the resist used does not provide sufficient resistance to subsequent etching steps to effectively transfer the desired pattern to the underlying layer. Thus, many practical examples (e.g., where an ultra thin resist layer is required, when the underlying material to be etched is thick, when a significant amount of etching depth is required, or where a certain etchant is used for a given underlying material) In this case, a so-called hard mask layer is used as an intermediate between the resist layer and the underlying material which can be patterned by transfer from the patterned resist. The hardmask layer must be able to withstand the etching process required to receive the pattern from the patterned resist layer and transfer the pattern to the underlying material.

Although many hardmask materials exist in the prior art, there is a continuing need for improved hardmask compositions. Many such prior art materials are difficult to apply to substrates, and therefore may require the use of, for example, chemical or physical vapor deposition, special solvents, or high temperature firing. It is desirable to have a hardmask composition that can be applied by spin-on application techniques without the need for high temperature firing. In addition, it can be easily etched selectively using the upper photosensitive resist layer as a mask, and at the same time having a hard mask composition resistant to the etching process required to pattern the lower layer using the hard mask layer as a mask when the lower layer is a metal layer. It is preferable. It is also desirable to provide adequate shelf life and to avoid inhibited interactions with the imaging resist layer (eg, by acid contamination from the hardmask). In addition, it is desirable to have a hardmask composition having certain optical properties for image radiation of shorter wavelengths (eg, 157, 193, 248 nm).

One embodiment of the present invention to provide a polymer having a strong absorbance in the short wavelength region of the DUV.

Another embodiment of the present invention is to provide a polymer composition having a strong absorbance in the short wavelength region of the DUV.

Another embodiment of the present invention includes the polymer composition, has high etching selectivity, sufficient resistance to multiple etching, minimizes the reflection between the resist and the underlying layer, and can be applied using a spin-on coating technique It is to provide a resist underlayer film composition.

Yet another embodiment of the present invention is to provide a patterning method of a material using the resist underlayer film composition.

The technical problems to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical problems not mentioned will be clearly understood by the average technician from the following description.

According to one embodiment of the present invention, a polymer having a repeating unit represented by Formula 1 is provided.

[Formula 1]

(In the formula 1,

,

,

,

,

,

,

,

,

,

및

의 방향족 고리 화합물로 이루어진 군에서 선택되고, Ar ₁ is

,

,

,

,

,

,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds,

In Formula 1, the left and right bonds of Ar ₁ may be located at any ring of the aromatic ring compound,

R ₁ to R ₃₉ are each independently selected from the group consisting of hydrogen, a hydroxy group (—OH), an alkyl group of C _1-10 , an aryl group of C _6-20 , an alkenyl group of C _2-10 , and a halogen atom,

N ₁ to n ₃₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring, and

,

,

,

및

의 방향족 고리 화합물을 포함하는 이무수물(dianhydride)로 이루어진 군에서 선택되고, Ar ₂ is -CRR'- or

,

,

,

And

Is selected from the group consisting of dianhydrides containing aromatic ring compounds of

In Formula 1, the left and right bonds of Ar ₂ may be located on any ring of the aromatic ring compound,

R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from

R ₁ to R ₃ , R ₁₀ to R ₁₃ , R ₃₃ to R ₃₆ , R ₆₁ and R ₆₂ are each independently hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom,

N ₁ to n ₃ , n ₁₀ to n ₁₃ , n ₃₃ to n ₃₆ , n ₆₁ and n ₆₂ each independently represent 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego,

Y is a single bond, -O-, -CO-, or -CW ₁ W _2- (W ₁ and W ₂ are each independently hydrogen, a hydroxyl group, a carboxylic acid group, -CF ₃ , C _1-10 An alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom.

Z ₁ to Z ₄ are each independently selected from the group consisting of hydrogen, a hydroxy group, a carboxylic acid group, -COR "and an aryl group of C _6-20 ,

R ″ is selected from the group consisting of hydrogen, carboxylic acid group, amine group, C _1-10 alkyl group, C _6-20 aryl group, C _2-10 alkenyl group and halogen atom.)

According to another embodiment of the invention, the first polymer having a repeating unit represented by the formula (1); And it provides a polymer composition comprising a second polymer having a repeating unit represented by the formula (2).

[Formula 2]

(In Formula 2,

,

,

,

, ,

,

,

,

및

의 방향족 고리 화합물로 이루어진 군에서 선택되고, Ar ₃ is ,

,

,

,

,,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds,

In Formula 2, the left and right bonds of Ar ₃ may be located at any ring of the aromatic ring compound,

R ₁ to R ₆ , R ₁₀ to R ₁₇ , R ₂₂ to R _36, and R ₄₀ to R ₄₉ are each independently hydrogen, a hydroxyl group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom,

N ₁ to n ₆ , n ₁₀ to n ₁₇ , n ₂₂ to n ₃₆ and n ₄₀ to n ₄₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. C.),

이고,X is -CRR'- or

ego,

R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from

Each R ₅₀ is independently selected from hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom,

N ₅₀ is 0 to 4)

According to another embodiment of the invention, (A) a polymer composition comprising a first polymer having a repeating unit represented by the formula (1); And (B) provides a resist underlayer film composition comprising an organic solvent.

According to another embodiment of the present invention, there is provided a method for manufacturing a material layer comprising: (a) providing a layer of material on a substrate; (b) forming a resist underlayer film using the resist underlayer film composition according to the present invention on the material layer; (c) forming a photosensitive imaging layer on the resist underlayer; (d) exposing the photosensitive imaging layer to radiation in a patterned manner to produce a pattern of areas exposed to radiation within the photosensitive imaging layer; (e) selectively removing the photosensitive imaging layer and the resist underlayer film to selectively expose the material layer; And (f) etching the exposed portion of the layer of material.

Other specific details of embodiments of the present invention are included in the following detailed description.

The polymer, the polymer composition, and the resist underlayer film composition including the same of the present invention have a refractive index and absorbance within a suitable range as an antireflection film in a DUV wavelength region such as ArF (193 nm) and KrF (248 nm) when forming a film. Reflectivity between the underlayers can be minimized, and the lithographic technique has a high etching selectivity and sufficient resistance to multiple etching, thereby providing an excellent lithographic structure in terms of pattern profile or margin.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise defined herein, "alkyl group" means an alkyl group of C _6-10 , "aryl group" means an aryl group of C _6-20 , and "alkenyl group" means an alkyl of C _6-10 . It means a kenyl group.

In the present specification, "substituted" means, unless otherwise defined, at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Cl, Br, or I), hydroxy group, nitro group, cyano group, amino group ( -NH ₂ , -NH (R), -N (R "') (R""),R"' and R "" are independently of each other an alkyl group of C _1-10 ), amidino group, hydrazine or hydra A substituted group, a carboxyl group, a substituted or unsubstituted C _1-10 alkyl group, a substituted or unsubstituted C _6-30 aryl group, a substituted or unsubstituted C _3-20 cycloalkyl group, a substituted or unsubstituted C _{3- It} means substituted with one or more substituents selected from the group consisting of a heteroaryl group of ₂₀ and a substituted or unsubstituted C _2-20 heterocycloalkyl group.

In addition, hetero herein means, unless otherwise defined, that the carbon atom is substituted with any one atom selected from the group consisting of N, O, S and P.

According to one embodiment of the present invention, a polymer having a repeating unit represented by Formula 1 is provided.

[Formula 1]

(In the formula 1,

,

,

,

,

,

,

,

,

,

및

의 방향족 고리 화합물로 이루어진 군에서 선택되고, Ar ₁ is

,

,

,

,

,

,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds,

In Formula 1, the left and right bonds of Ar ₁ may be located at any ring of the aromatic ring compound,

R ₁ to R ₃₉ are each independently selected from the group consisting of hydrogen, a hydroxy group (—OH), an alkyl group of C _1-10, an aryl group of C _6-20 , an alkenyl group of C _2-10 , and a halogen atom; ,

N ₁ to n ₃₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring, and

,

,

,

및

의 방향족 고리 화합물을 포함하는 이무수물(dianhydride)로 이루어진 군에서 선택되고, Ar ₂ is -CRR'- or

,

,

,

And

Is selected from the group consisting of dianhydrides containing aromatic ring compounds of

In Formula 1, the left and right bonds of Ar ₂ may be located on any ring of the aromatic ring compound,

R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from

R ₁ to R ₃ , R ₁₀ to R ₁₃ , R ₃₃ to R ₃₆ , R ₆₁ and R ₆₂ are each independently hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom,

N ₁ to n ₃ , n ₁₀ to n ₁₃ , n ₃₃ to n ₃₆ , n ₆₁ and n ₆₂ each independently represent 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego,

Y is a single bond, -O-, -CO-, or -CW ₁ W _2- (W ₁ and W ₂ are each independently hydrogen, a hydroxyl group, a carboxylic acid group, -CF ₃ , C _1-10 An alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom.

Z ₁ to Z ₄ are each independently selected from the group consisting of hydrogen, a hydroxy group, a carboxylic acid group, -COR "and an aryl group of C _6-20 ,

R ″ is selected from the group consisting of hydrogen, carboxylic acid group, amine group, C _1-10 alkyl group, C _6-20 aryl group, C _2-10 alkenyl group and halogen atom.)

K is the number of H that may be present when there is no substituent other than the two-side bond group connected to the main chain of Formula 1 in each of the aromatic rings applicable to Ar ₁ and Ar ₂ (that is, the substituents may be bonded to the aromatic ring). Equal to the number of joins present).

In addition, according to another embodiment of the present invention, the first polymer having a repeating unit represented by Formula 1; And it provides a polymer composition comprising a second polymer having a repeating unit represented by the formula (2).

[Formula 2]

(In Formula 2,

,

,

,

,

, ,

,

,

,

및

의 방향족 고리 화합물로 이루어진 군에서 선택되고, Ar ₃ is

,

,

,

,

,,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds,

In Formula 2, the left and right bonds of Ar ₃ may be located at any ring of the aromatic ring compound,

R ₁ to R ₆ , R ₁₀ to R ₁₇ , R ₂₂ to R _36, and R ₄₀ to R ₄₉ are each independently hydrogen, a hydroxyl group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom,

N ₁ to n ₆ , n ₁₀ to n ₁₇ , n ₂₂ to n ₃₆ and n ₄₀ to n ₄₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego,

이고, X is -CRR'- or

ego,

R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from

Each R ₅₀ is independently selected from hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom,

N ₅₀ is 0 to 4)

K is the number of H that may be present in the case where there is no substituent other than the two-sided bond group connected to the main chain of Formula 2 among each of the aromatic rings applicable to Ar ₃ (that is, Equal to number).

The second polymer having a repeating unit represented by Formula 2 is preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight, relative to 100 parts by weight of the first polymer having a repeating unit represented by Formula 1 above. When the second polymer is in the range of 10 to 100 parts by weight, there is an effect of implementing the desired thickness or good thin film during coating.

The polymer and the polymer composition contain an aromatic ring having strong absorption in the short wavelength region of the DUV (particularly, 248 nm), thereby minimizing reflectivity and good etching resistance.

According to another embodiment of the present invention, a polymer composition comprising a first polymer having a repeating unit represented by Formula 1; And it provides a resist underlayer film composition comprising an organic solvent.

In the resist underlayer film composition of the present invention, the aromatic ring of the polymer composition is preferably present in the skeleton portion of the polymer. The aromatic ring absorbs a short wavelength (193nm, 248nm) of the radiation in the lithographic process, it is possible to minimize the reflectivity without a separate anti-reflective coating when using the resist underlayer film composition of the present invention. On the other hand, the polymer composition preferably contains a plurality of reactive sites, that is, hydroxy groups distributed along the polymer reacting with the crosslinking component. Therefore, when the resist underlayer film composition of the present invention includes a crosslinking component, curing of the composition may be accelerated by an additional crosslinking reaction in addition to the self-crosslinking reaction.

In addition, the resist underlayer film composition of the present invention has a solution and film-forming property which helps to form a layer by conventional spin coating.

The polymer composition may further include a second polymer having a repeating unit represented by Chemical Formula 2.

The polymer composition used in the resist underlayer film composition of the present invention preferably has a weight average molecular weight of 1,000 to 30,000, more preferably 1,000 to 10,000. When the weight average molecular weight of the polymer composition is in the range of 1,000 to 30,000, there is an effect of implementing the desired coating thickness or a good thin film.

The polymer composition is preferably used in 1 to 30 parts by weight with respect to 100 parts by weight of the organic solvent, more preferably 1 to 27 parts by weight. When the polymer composition is less than 1 part by weight or used in excess of 30 parts by weight, it is difficult to match the exact coating thickness because it is less than or exceeds the desired coating thickness.

The organic solvent is not particularly limited as long as it is an organic solvent having sufficient solubility in the polymer composition. For example, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (propylene). glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate, gamma butyl lactone (GBL), acetyl acetone, and the like.

In addition, the resist underlayer film composition of the present invention further comprises a crosslinking component; And an acid catalyst.

The crosslinking component is preferably capable of crosslinking the repeating unit of the polymer by heating in a reaction catalyzed by the generated acid, and the crosslinking component may include a melamine resin, an amino resin, a glycoluryl compound, and a bisepoxy compound. It is preferred to use any one selected from the group consisting of, and is not particularly limited as long as it is a crosslinking agent capable of reacting with a hydroxyl group of the polymer composition in a manner that can be catalyzed by the resulting acid.

Specific examples of the crosslinking component that can be used in the resist underlayer film composition of the present invention include etherified amino resins such as methylated or butylated melamine resins (specific examples of which are N-methoxymethyl-melamine resins or N-butoxymethyl-melamine resin) and methylated or butylated urea resin (specific examples include Cymel U-65 Resin or UFR-80 Resin from CYTEC), glycoluril derivatives represented by Formula 3 Examples include Powderlink 1174, CYTEC Co.), 2,6-bis (hydroxymethyl) -p-cresol compound) and the like. In addition, the bisepoxy-based compound represented by the following formula (4) and the melamine derivative represented by the formula (5) can also be used as a crosslinking component.

(3)

[Formula 4]

[Chemical Formula 5]

The acid catalyst used in the resist underlayer film composition of the present invention is preferably a heat activated acid catalyst.

As the acid catalyst, an organic acid such as p-toluene sulfonic acid monohydrate (p-toluene sulfonic acid monohydrate) may be used, and a compound of a TAG (thermal acid generator) system having a storage stability can be used as a catalyst. TAG is an acid generator compound intended to release acid upon heat treatment, for example pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone , Benzointosylate, 2-nitrobenzyltosylate, alkyl esters of euphonic acid, and the like are preferably used. In addition, other photosensitive acid catalysts known in the resist art can be used as long as they are compatible with the other components of the antireflective composition.

When the crosslinking component and the acid catalyst are further included, the hard mask composition of the present invention comprises (A) 1 to 20% by weight of the polymer composition, more preferably 3 to 10% by weight, (B) 75 to 98.8 organic solvents. It is preferred to include by weight%, (C) 0.1 to 5% by weight of the crosslinking component, more preferably 0.1 to 3% by weight and (D) acid catalyst 0.001 to 0.05% by weight, more preferably 0.001 to 0.03% by weight. .

When the polymer composition is less than 1% by weight or more than 20% by weight, and when the organic solvent is less than 75% by weight or more than 98.8% by weight, it becomes less than or exceeds the desired coating thickness, making it difficult to attain an accurate coating thickness. .

When the crosslinking component is less than 0.1% by weight, the crosslinking property may not appear. When the crosslinking component is more than 5% by weight, the optical properties of the coating film may be changed by an excessive injection. When the acid catalyst is less than 0.001% by weight, the crosslinking property may be If not exceeding 0.05% by weight, storage stability may be affected by increased acidity due to overdose.

According to another embodiment of the present invention, a method of patterning a material using the resist underlayer film composition as described above is provided.

Specifically, the patterning method of the material,

(a) providing a layer of material on the substrate;

(b) forming a resist underlayer film using the resist underlayer film composition according to the present invention on the material layer;

(c) forming a photosensitive imaging layer on the resist underlayer;

(d) exposing the photosensitive imaging layer to radiation in a patterned manner to produce a pattern of areas exposed to radiation within the photosensitive imaging layer;

(e) selectively removing the photosensitive imaging layer and the resist underlayer film to selectively expose the material layer; And

(f) etching the exposed portion of the material layer.

The method may further include forming a silicon-containing resist underlayer film (second underlayer film) on the resist underlayer film (first underlayer film) layer before the step (c) of the patterning method of the material. The method may further include forming a bottom anti-refractive coating (BARC) layer before the step (c) after the silicon-containing resist underlayer (second lower layer) layer is formed.

The method of patterning the material on the substrate according to the invention can be carried out specifically as follows.

First, a material to be patterned, such as aluminum and SiN (silicon nitride), is formed on a silicon substrate according to a conventional method. The material to be patterned in which the resist underlayer film composition of the present invention is used may be any conductive, semiconductive, magnetic or insulating material.

Subsequently, using the resist underlayer film composition of this invention, it spin-coats to thickness of 500-4,000 kPa, and bakes at 100-300 degreeC for 10 second-10 minutes, and forms a resist underlayer film. In this case, the thickness of the resist underlayer film, the baking temperature and time is not limited to the above range, but may be manufactured in a variety of different forms, those skilled in the art to which the present invention belongs However, it will be understood that other specific forms may be practiced without changing the essential features.

When the resist underlayer film is formed, a photosensitive imaging layer is formed, and a development process of exposing a region where a pattern is to be formed is performed by an exposure process through the photosensitive imaging layer.

Subsequently, the photosensitive imaging layer and the resist underlayer film are selectively removed to expose a portion of the material layer, and generally dry etching is performed using a CHF ₃ / CF ₄ mixed gas or the like.

After the material is patterned, any remaining resist can be removed by conventional photosensitive resist strippers.

By this method, a semiconductor integrated circuit device can be provided.

Thus, the compositions of the present invention and formed lithographic structures can be used in the manufacture and design of integrated circuit devices in accordance with semiconductor fabrication processes. For example, it can be used to form patterned material layer structures such as metal wiring, holes for contacts or bias, insulating sections (e.g., damascene trenches or shallow trench isolation (STI)), trenches for capacitor structures, and the like. Can be. It is also to be understood that the invention is not limited to any particular lithographic technique or device structure.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples and comparative examples are for illustrative purposes only and are not intended to limit the present invention.

[Polymerization of Polymer]

Synthesis Example 1 Polymer obtained by polymerizing fluorenylidene dinaphthol with {4- [4- (hydroxy-pyrene-phenyl-methyl) phenoxy] phenyl} diphenylmethanol

[Formula 6]

A 1 L four-necked flask equipped with a condenser, a nitrogen gas introduction tube, a mechanical stirrer, and a 300 ml dropping funnel was prepared and placed in an oil bath at 80 ° C. Constant temperature and stirring with magnets were performed on a hotplate, and the cooling water temperature of the condenser was fixed at 5 ° C. 18 g of 0.04 mol of fluorenylidene dinaphthol and 31.3 g of 0.04 mol of {4- [4- (hydroxy-pyrene-phenyl-methyl) phenoxy] phenyl} diphenylmethanol were charged into a four-necked flask (reactor) and 100 ml. After dissolving in propylene glycol monomethyl ether acetate (PGMEA), and completely dissolved, 0.2 g of 0.05 mol of sulfuric acid was added and stirred at 100 ° C. for 12 hours to polymerize.

The reaction time was determined by measuring the weight average molecular weight at regular intervals. (A sample for measuring the weight average molecular weight was sampled with 1g of the reactant and quenched to room temperature, and then 0.02g was taken as the solvent. Tetrahydrofuran (THF) was used to dilute the solids to 4% by weight.)

The reaction was then slowly cooled to room temperature.

After completion of the reaction, an acid, an unreacted monomer and a low molecular weight were removed using a distilled water / methanol (MeOH) mixed solvent in a weight ratio of 1:10, and then filtered to obtain a solid polymer. Subsequently, the solid polymer was dissolved in PGMEA, and then low molecular weight containing monomers was removed using MeOH.

The weight average molecular weight and the polydispersity of the obtained polymer were measured by gas phase chromatography (GPC) under THF to obtain a polymer represented by Chemical Formula 6 having a weight average molecular weight of 1,800 and a dispersion degree of 2.5.

Synthesis Example 2 Polymers Polymerized with Fluorenylidenedynaphthol and [4- (hydroxy-diphenyl-methyl) phenyl] diphenylmethanol

[Formula 7]

31.3 g of 0.04 mol {4- [4- (hydroxy-pyrene-phenyl-methyl) phenoxy] phenyl} diphenylmethanol was added to the reactor and stirred for 12 hours, instead of polymerization to produce 0.04 mol of [4- 17.7 g of (hydroxy-diphenyl-methyl) phenyl] diphenylmethanol was added to the reactor, followed by stirring for 24 hours to polymerize in the same manner as in Synthesis Example 1, except that the weight average molecular weight represented by Formula 7 was 2,000. And a polymer having a dispersion degree of 2.3 was polymerized.

Synthesis Example 3 Polymers Polymerized with Hydroxypyrene and [4- (hydroxy-diphenyl-methyl) phenyl] diphenylmethanol

[Formula 8]

18 g of 0.04 mol of fluorenylidene dinaphthol and 31.3 g of 0.04 mol of {4- [4- (hydroxy-pyrene-phenyl-methyl) phenoxy] phenyl} diphenylmethanol were added to the reactor and stirred for 12 hours to polymerize. Instead of this, 8.8 g of 0.04 mol of hydroxypyrene and 17.7 g of 0.04 mol of [4- (hydroxy-diphenyl-methyl) phenyl] diphenylmethanol were added to the reactor and stirred for 24 hours to polymerize. In the same manner as in Synthesis Example 1 was polymerized a polymer having a weight average molecular weight of 2,200 and a degree of dispersion of 2.2.

Synthesis Example 4 Polymer Polymerized with Fluorenylidenediphenol and α, α'-dichloro-p-xylene

[Chemical Formula 9]

8.75 g (0.05 mol) of α, α'-dichloro-p-xylene and aluminum chloride were introduced into a 1 liter four-necked flask equipped with a mechanical stirrer, a cooling tube, a 300 ml dropping funnel and a nitrogen gas introduction tube. ) 26.66 g and 200 g of γ-butyrolactone were added and stirred. After 10 minutes, a solution of 35.03 g (0.10 mol) of 4,4 '-(9-fluorenylidene) diphenol in 200 g of γ-butyrolactone was slowly added dropwise for 30 minutes, followed by reaction for 12 hours. . After completion of the reaction, the acid was removed using water, and then concentrated by an evaporator. It was then diluted with MAK and MeOH and adjusted to a solution of 15 wt% MAK / MeOH = 4/1 (weight ratios). The solution was placed in a 3 L separatory funnel, and n-heptane was added thereto to remove the low molecular weight containing the monomer to obtain a polymer represented by the formula (9) having a weight average molecular weight of 12,000 and a dispersity of 2.0.

[Manufacture of resist underlayer film composition]

(Examples 1 to 3)

1.0 g of the polymers prepared in Synthesis Examples 1 to 3 were respectively weighed, and 0.1 g of a crosslinking agent (Powderlink 1174, CYTEC Co., Ltd.) and 100 mg of pyridinium p-toluene sulfonate represented by the following Formula 3 were used: 9 g of PGMEA. After dissolving in filtration, the resist underlayer film compositions of Examples 1 to 3 were prepared, respectively.

(3)

(Comparative Example 1)

1.0 g of the polymer prepared in Synthesis Example 4, 0.1 g of a crosslinking agent (Cymel 303, CYTEC) and 100 mg of pyridinium p-toluene sulfonate were dissolved in PGMEA 9 g, and then filtered to prepare a resist underlayer film composition.

[Optical Property Evaluation]

The resist underlayer film compositions prepared in Examples 1 to 3 and Comparative Example 1 were each spin-coated on a silicon wafer and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1,500 mm 3.

The n value (refractive index) and the k value (extinction coefficient) of the formed films were obtained, respectively. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1 below.

[Table 1]

As a result of evaluating the optical properties of the resist underlayer film compositions of Examples 1 to 3, it was confirmed that the refractive index and the absorbance of the antireflection film were suitable in the ArF (193 nm) and KrF (248 nm) wavelength ranges.

[Application to anti-reflection hard mask layer]

(Examples 4 to 6)

Each of the resist underlayer film compositions of Examples 1 to 3 was coated on a silicon wafer coated with aluminum by spin-coating and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1,500 mm 3 of Examples 4 to 6.

(Comparative Example 2)

The sample solution prepared in Comparative Example 1 was coated on a silicon wafer coated with aluminum by spin-coating, and baked at 200 ° C. for 60 seconds to form a film having a thickness of 1,500 mm in Comparative Example 2.

[Pattern Characteristic Evaluation]

Coat the photosensitive resist for KrF on each film of Examples 4 to 6 and Comparative Example 2, bake at 110 ° C. for 60 seconds, and expose each using an exposure equipment of ASML (XT: 1400, NA 0.93), followed by TMAH (2.38wt). % Aqueous solution). The line and space pattern of 90 nm was observed using a field emission scanning electron microscope (FE-SEM), and the exposure latitude (EL) margin and the light source according to the change of the exposure amount were measured. DoF (depth of focus) margin was observed according to the distance variation of and recorded in Table 2.

[Table 2]

As a result of the pattern evaluation of Examples 4-6, the favorable result was confirmed in a pattern form and a margin. However, in the case of Comparative Example 2, an under-cut pattern appeared, and the EL margin and the DoF margin were confirmed to be relatively low, which may be due to the difference in absorption characteristics at KrF (248 nm) wavelength. do.

[Evaluation]

Each film of Examples 4 to 6 and Comparative Example 2 was dry etched using CHF ₃ / CF ₄ mixed gas, and then dry etched again using BCl ₃ / Cl ₂ mixed gas. Finally, the remaining organics were removed using O ₂ gas, and the cross sections were observed with FE-SEM, and the results are shown in Table 3.

[Table 3]

As a result of the etch evaluation of Examples 4-6, the favorable etch profile and selectivity were confirmed. However, in the case of Comparative Example 2, the tapered pattern shape was shown after the etch, which is considered to be insufficient in the selectivity under the etch conditions.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (18)

A polymer having a repeating unit represented by the following formula (1). [Formula 1]

(In the formula 1, Ar ₁ is

,

,

,

,

,

,

,

, Aromatic ring compounds of, and In Formula 1, the left and right bonds of Ar ₁ may be located at any ring of the aromatic ring compound, R ₁ to R ₃₉ are each independently selected from the group consisting of hydrogen, a hydroxy group (—OH), an alkyl group of C _1-10 , an aryl group of C _6-20 , an alkenyl group of C _2-10 , and a halogen atom, N ₁ to n ₃₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring, and Ar ₂ is -CRR'- or

,

,

,

And

Is selected from the group consisting of dianhydrides containing aromatic ring compounds of In Formula 1, the left and right bonds of Ar ₂ may be located on any ring of the aromatic ring compound, R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from R ₁ to R ₃ , R ₁₀ to R ₁₃ , R ₃₃ to R ₃₆ , R ₆₁ and R ₆₂ are each independently hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom, N ₁ to n ₃ , n ₁₀ to n ₁₃ , n ₃₃ to n ₃₆ , n ₆₁ and n ₆₂ each independently represent 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego, Y is a single bond, -O-, -CO-, or -CW ₁ W _2- (W ₁ and W ₂ are each independently hydrogen, a hydroxyl group, a carboxylic acid group, -CF ₃ , C _1-10 An alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom. Z ₁ to Z ₄ are each independently selected from the group consisting of hydrogen, a hydroxy group, a carboxylic acid group, -COR "and an aryl group of C _6-20 , R ″ is selected from the group consisting of hydrogen, carboxylic acid group, amine group, C _1-10 alkyl group, C _6-20 aryl group, C _2-10 alkenyl group and halogen atom.) The method of claim 1, At least one of Z ₁ to Z ₄ of Formula 1 is an aryl group. Claim 1 polymer having a repeating unit represented by the formula (1) described in claim 1; And A polymer composition comprising a second polymer having a repeating unit represented by the formula (2). [Formula 2]

(In Formula 2, Ar ₃ is

,

,

,

,

,,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds, In Formula 2, the left and right bonds of Ar ₃ may be located at any ring of the aromatic ring compound, R ₁ to R ₆ , R ₁₀ to R ₁₇ , R ₂₂ to R _36, and R ₄₀ to R ₄₉ are each independently hydrogen, a hydroxyl group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom, N ₁ to n ₆ , n ₁₀ to n ₁₇ , n ₂₂ to n ₃₆ and n ₄₀ to n ₄₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. C.), X is -CRR'- or

ego, R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from Each R ₅₀ is independently selected from hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom, N ₅₀ is 0 to 4) The method of claim 3, The second polymer having a repeating unit represented by the formula (2) is 10 to 100 parts by weight relative to 100 parts by weight of the first polymer having a repeating unit represented by the formula (1). (A) a polymer composition comprising a first polymer having a repeating unit represented by the following formula (1); And (B) organic solvent A resist underlayer film composition comprising a. [Formula 1]

(In the formula 1, Ar ₁ is

,

,

,

,

,

,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds, In Formula 1, the left and right bonds of Ar ₁ may be located at any ring of the aromatic ring compound, R ₁ to R ₃₉ are each independently selected from the group consisting of hydrogen, a hydroxy group (—OH), an alkyl group of C _1-10 , an aryl group of C _6-20 , an alkenyl group of C _2-10 , and a halogen atom, N ₁ to n ₃₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring, and Ar ₂ is -CRR'- or

,

,

,

And

Is selected from the group consisting of dianhydrides containing aromatic ring compounds of In Formula 1, the left and right bonds of Ar ₂ may be located on any ring of the aromatic ring compound, R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from R ₁ to R ₃ , R ₁₀ to R ₁₃ , R ₃₃ to R ₃₆ and R ₆₁ to R ₆₂ are each independently hydrogen, a hydroxyl group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom, N ₁ to n ₃ , n ₁₀ to n ₁₃ , n ₃₃ to n ₃₆ and n ₆₁ to n ₆₂ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego, Y is a single bond, -O-, -CO-, or -CW ₁ W _2- (W ₁ and W ₂ are each independently hydrogen, a hydroxyl group, a carboxylic acid group, -CF ₃ , C _1-10 An alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom. Z ₁ to Z ₄ are each independently selected from the group consisting of hydrogen, a hydroxy group, a carboxylic acid group, -COR "and an aryl group of C _6-20 , R ″ is selected from the group consisting of hydrogen, carboxylic acid group, amine group, C _1-10 alkyl group, C _6-20 aryl group, C _2-10 alkenyl group and halogen atom.) The method of claim 5, At least one of Z ₁ to Z ₄ of the general formula (1) is an aryl group resist resist layer composition. The method of claim 5, The polymer composition is a resist underlayer film composition having a weight average molecular weight of 1,000 to 30,000. The method of claim 5, The polymer composition further comprises a second polymer having a repeating unit represented by the formula (2). [Formula 2]

(In Formula 2, Ar ₃ is

,

,

,

,

,,

,

,

,

And

Is selected from the group consisting of aromatic ring compounds, In Formula 2, the left and right bonds of Ar ₃ may be located at any ring of the aromatic ring compound, R ₁ to R ₆ , R ₁₀ to R ₁₇ , R ₂₂ to R _36, and R ₄₀ to R ₄₉ are each independently hydrogen, a hydroxyl group, a C _1-10 alkyl group, a C _6-20 aryl group, C ₂ An alkenyl group of _-10 and a halogen atom, N ₁ to n ₆ , n ₁₀ to n ₁₇ , n ₂₂ to n ₃₆ and n ₄₀ to n ₄₉ are each independently 0 to k, where k corresponds to the number of H that may be present in each aromatic ring. .)ego, X is -CRR'- or

ego, R and R 'are each independently a group consisting of hydrogen, a hydroxy group, a carboxylic acid group (-COOH), an amine group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group and a halogen atom Selected from Each R ₅₀ is independently selected from hydrogen, a hydroxy group, a C _1-10 alkyl group, a C _6-20 aryl group, a C _2-10 alkenyl group, and a halogen atom, N ₅₀ is 0 to 4) 9. The method of claim 8, The second polymer having a repeating unit represented by the formula (2) is 10 to 100 parts by weight relative to 100 parts by weight of the first polymer having a repeating unit represented by the formula (1). The method of claim 5, The resist underlayer film composition is (C) crosslinking component; And (D) acid catalyst The resist underlayer film composition further comprises. The method of claim 10, The resist underlayer film composition is (A) 1 to 20% by weight of the polymer composition; (B) 75 to 98.8% by weight of an organic solvent; (C) 0.1 to 5% by weight crosslinkable; And (D) 0.001 to 0.05% by weight of acid catalyst Resist underlayer film composition comprising a. The method of claim 10, The crosslinking component is a resist underlayer film composition, characterized in that any one selected from the group consisting of a melamine resin, an amino resin, a glycoluril compound and a bis epoxy compound. The method of claim 10, The acid catalyst is p-toluene sulfonic acid monohydrate, pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromo cyclohexadienone, A resist underlayer film composition selected from the group consisting of benzoin tosylate, 2-nitrobenzyl tosylate and alkyl esters of euphonic acid. The method of claim 5, The resist underlayer film composition further comprises a surfactant. (a) providing a layer of material on the substrate; (b) forming a resist underlayer film using the resist underlayer film composition according to any one of claims 5 to 14 on the material layer; (c) forming a photosensitive imaging layer on the resist underlayer; (d) exposing the photosensitive imaging layer to radiation in a patterned manner to produce a pattern of areas exposed to radiation within the photosensitive imaging layer; (e) selectively removing the photosensitive imaging layer and the resist underlayer film to selectively expose the material layer; And (f) etching the exposed portion of the material layer. The method of claim 15, Before the step (c) of the patterning method of the material, further comprising forming a silicon-containing resist underlayer film (second underlayer film) layer on the resist underlayer film (first underlayer film) layer. Patterning method of material to make. 17. The method of claim 16, After forming the silicon-containing resist underlayer (second underlayer) layer, and further comprising forming a bottom anti-refractive coating (BARC) layer before step (c). Patterning method of the material. The method of claim 15, And the method of patterning the material is a method of manufacturing a semiconductor integrated circuit device.