KR20100080140A - High etch resistant polymer having aromatic rings, composition containing the same,d of patterning materials using the same - Google Patents

Abstract

PURPOSE: An aromatic ring-containing polymer is provided to ensure high etching selectivity and to minimize reflection between the resist and backside layer. CONSTITUTION: An aromatic ring-containing polymer contains a repeat unit of chemical formulas 1 and 2. In chemical formula 1, R1-R3 are different or same hydrogen, hydroxyl group, halogen, substituted or non-substituted alkyl group, substituted or non-substituted aryl group, and substituted or non-substituted heteroaryl; x is 0 or 1; y is 03 integer; z is 0-2 integer; and A is substituted or non-substituted straight or branched alkylene group.

Description

High-etching aromatic ring-containing polymer, a composition for resist underlayer film containing the same, and a patterning method of the material using the same.

The present invention relates to a highly etch resistant aromatic ring-containing polymer, a composition for resist underlayer film comprising the same, and a patterning method of a material using the same. More particularly, the present invention has a very excellent antireflection property, mechanical property, and etching selectivity property. The present invention relates to an aromatic ring-containing polymer, a composition for resist underlayer film useful for a lithographic process for forming a micropattern including the same, and applicable to a spin-on coating technique, and to a patterning method of a material using the same.

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 the 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 exposing the radiation-sensitive 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 backing 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 antireflective coating (ARC) to minimize the reflectivity between the imaging layer, such as a layer of radiation sensitive resist material and backing 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 a desired pattern to the layer behind the resist. Thus, many practical examples (e.g., where an ultra thin resist layer is required, when the backing material to be etched is thick, when a significant amount of etching depth is required, and / or where an etchant specific to a given backing material is required) In the case where it is necessary to use), a so-called hardmask layer is used as an intermediate layer between the resist layer and the backing 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 backing 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 chemical or physical deposition, special solvents, and / or high temperature firing, for example. It is desirable to have a hardmask composition that can be applied by spin-coating techniques without the need for high temperature firing. In addition, the hard mask composition can be easily and easily etched using the upper photoresist layer as a mask, and at the same time resistant to the etching process required to pattern the back layer using the hard mask layer as a mask when the back layer is a metal layer. It is preferable to have. 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).

In conclusion, it is desirable to perform lithographic techniques using anti-reflective compositions that have high etch selectivity, sufficient resistance to multiple etching, and minimize reflectivity between the resist and backing layer. This lithographic technology will enable the production of very detailed semiconductor devices.

One embodiment of the present invention aims to provide an aromatic ring-containing polymer having high etching selectivity, sufficient resistance to multiple etching, and minimizing the reflectivity between the resist and the backing layer.

According to another embodiment of the present invention, in performing a lithographic technique using the composition for a resist underlayer film containing the aromatic ring-containing polymer, coating is possible using a spin-on application technique. In addition, it is an object to provide a composition comprising said polymer with minimal or no acid contaminant content.

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

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

According to one embodiment of the present invention, an aromatic ring-containing polymer including a repeating unit represented by the following Chemical Formula 1 and Chemical Formula 2 is provided.

[Formula 1]

(In the formula 1,

R₁ to R₃ are the same as or different from each other, and each independently hydrogen; Hydroxy group halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group,

x is 0 or 1,

y is an integer from 0 to 3,

z is an integer of 0 to 2).

[Formula 2]

(In Formula 2,

A is a substituted or unsubstituted linear or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of one or more -CH 2-substituted or unsubstituted arylene groups, alkenylene groups and azo groups. Can be.)

According to another embodiment of the present invention, there is provided a composition for resist underlayer film comprising (a) an aromatic ring-containing polymer or a mixture thereof and (b) an organic solvent.

According to yet another embodiment of the present invention, there is provided a method for producing a layer of material, comprising: (a) providing a layer of material on a substrate; (b) forming a resist underlayer film using the composition for resist underlayer film according to the present invention over the material layer; (c) forming a radiation-sensitive imaging layer over the resist underlayer; (d) generating a pattern of radiation-exposed areas within the radiation-sensitive imaging layer by patterning the radiation-sensitive imaging layer to radiation; (e) selectively removing portions of the radiation-sensitive imaging layer and the resist underlayer film to expose portions of the material layer and (f) etching the exposed portions of the material layer. It provides a method for producing a patterned material shape.

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

The aromatic ring-containing polymer according to an embodiment of the present invention and the composition for resist underlayer film containing the same are useful for use as an anti-reflection film in a deep UV (DUV) region such as an ArF (193 nm) and KrF (248 nm) wavelength region when forming a film. By having a range of refractive index and absorbance it is possible to minimize the reflectivity between the resist and the back layer. It is possible to provide a lithographic structure having high etching selectivity and sufficient resistance to multiple etching when performing lithographic technology, which has excellent pattern evaluation results in terms of pattern profile or margin. The advantage is minimal or no.

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.

As used herein, unless otherwise defined, the term "substituted" means substituted with a substituent selected from the group consisting of an alkyl group, a halogen group, a haloalkyl group, an aryl group, and a heteroaryl group.

In the present specification, "hetero" means one to three hetero atoms selected from the group consisting of N, O, S, and P in one ring group, unless otherwise defined. .

Unless otherwise defined herein, an "alkyl group" is an alkyl group having 1 to 12 carbon atoms, more preferably a lower alkyl group having 1 to 8 carbon atoms, and an "alkylene group" is an alkylene group having 2 to 30 carbon atoms. More preferably an alkylene group having 2 to 20 carbon atoms and an "alkoxy group" means an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms and an "aldehyde group". An aldehyde group of 12 to 12, more preferably an aldehyde group having 1 to 8 carbon atoms, and an "aryl group" means an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and an "arylene group" Is an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 20 carbon atoms, and a "heteroaryl group" is selected from the group consisting of N and P in an aromatic ring having 2 to 30 carbon atoms. Hetero member And a heteroaryl group containing 1 to 3 carbon atoms, and more preferably, a heteroaryl group containing 1 to 3 heteroatoms in an aromatic ring having 2 to 20 carbon atoms, and is referred to as a "halogen group". F, Cl, Br, and I, and more preferably F or Cl.

According to one embodiment of the invention, there is provided an aromatic ring-containing polymer comprising a repeating unit represented by the following formula (1) and (2).

[Formula 1]

(In the formula 1,

R₁ to R₃ are the same as or different from each other, and each independently hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group,

x is 0 or 1,

y is an integer from 0 to 3,

z is an integer of 0 to 2).

[Formula 2]

(In Formula 2,

A is a substituted or unsubstituted linear or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of one or more -CH 2-substituted or unsubstituted arylene groups, alkenylene groups and azo groups. Can be.)

A is preferably an alkylene group substituted with an aryl group.

The aromatic ring-containing polymer including the repeating units represented by Formula 1 and Formula 2 may be arranged in any order or in the form of a block copolymer or an alternating copolymer.

In addition, the aromatic ring-containing polymer is good because it can have more excellent solubility when including the repeating units represented by the formula (1) and formula (2) in the molar ratio of 1: 1 to 2.

The aromatic ring-containing polymer is more preferable when it is represented by the following formula (3).

(3)

(In Formula 3, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; hydroxy group; halogen group substitution; or unsubstituted alkyl group; substituted or unsubstituted aryl group; and substituted or unsubstituted heteroaryl And A is a substituted or unsubstituted straight or branched alkylene group, wherein said alkylene group is optionally composed of one or more -CH 2-substituted or unsubstituted arylene groups, alkenylene groups and azo groups A substituent selected from the group, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2, n is an integer ranging from 2 ≤ n <100.)

In particular, in the above formulas (1), (2) or (3), when at least one of R ₁ to R ₃ is substituted with a hydroxy group, it is more preferable since there is an advantage in terms of improving the degree of crosslinking and coating properties.

In addition, A is more preferable because it has advantages such as solubility improvement when selected from the group consisting of substituents represented by the following Chemical Formulas 4 and 5.

[Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 4 and 5,

A¹ to A³ is a substituted or unsubstituted alkylene group,

Ar 'is substituted or unsubstituted phenylene group substituted or unsubstituted biphenylene group substituted or unsubstituted terphenylene group substituted or unsubstituted naphthylene group substituted or unsubstituted anthracene substituted or unsubstituted pyrene group substituted or unsubstituted It is selected from the group consisting of a substituted stilbene group and a substituted or unsubstituted azobenzene group,

Ar₂ is selected from the group consisting of a substituted or unsubstituted phenyl group and a substituted or unsubstituted phenol group,

n is 0 or an integer of 1 to 2)

More specifically, A may be selected from a compound represented by the following formula (6).

[Formula 6]

The weight average molecular weight of the aromatic ring-containing polymer is in the range of 2,000 to 10,000 may be more preferably used in terms of solubility improvement and out gas development. Even more preferably, it may be used in the range of 4,000 to 10,000.

In addition, the aromatic ring-containing polymer may be used in the range of 1.2 to 2.5 polydispersity in order to obtain the advantage that the same physical properties are easily reproduced. More preferably, it can be used in the range of 2.1 to 2.5.

The monomer for obtaining the aromatic ring-containing polymer according to the present invention is generally used in the art and is not particularly limited. Any monomer may be used as long as the monomer can obtain the aromatic ring-containing polymer according to the present invention. More preferred examples of the monomer may be obtained by mixing and polymerizing pyrene or a substituted or unsubstituted pyrene derivative with a derivative containing a substituted or unsubstituted aldehyde, alkoxy or hydroxy group.

As a more specific example of the said monomer, the monomer represented by following formula (7) and (8) is mentioned.

[Formula 7]

(In Chemical Formula 7,

R₁ to R₃ are the same as or different from each other, and each independently hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group,

x is 0 or 1,

y is an integer from 0 to 3,

z is an integer from 0 to 2,

X 'to X' are the same as or different from each other, and each independently selected from the group consisting of a hydroxyl group aldehyde group and an alkoxy group,

n 'through n' are integers from 0 to 2, and n 'through n' cannot all be zero.)

[Formula 8]

(In Formula 8,

A is a substituted or unsubstituted linear or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of one or more -CH 2-substituted or unsubstituted arylene groups, alkenylene groups and azo groups. Can,

X ₅ and X ₆ are the same as or different from each other, and each independently selected from the group consisting of a hydroxyl group aldehyde group and an alkoxy group,

n ₅ to n ₆ are integers from 0 to 2, and n ₅ to n ₆ cannot all be zero.)

Aromatic ring-containing polymers and mixtures thereof provided by the present invention include aromatic rings in the backbone portion of the polymer in which each polymer has a strong absorption in the short wavelength region (especially 193, 248 nm). Thus, the aromatic ring containing polymers according to the invention have strong absorption in the short wavelength range (eg 157, 193, 248 nm, in particular 248 nm).

According to another embodiment of the present invention, there is provided a composition for a resist underlayer film comprising (a) the aromatic ring-containing polymer according to the present invention or a mixture thereof and (b) an organic solvent. At this time, the characteristic of the aromatic ring-containing polymer is as described while explaining the aromatic ring-containing polymer.

In the case of the polymer, even if a special catalyst is not used, the crosslinking reaction can be performed only under high temperature conditions, and thus there is an advantage of preventing contamination by a catalyst, particularly an acid.

In the composition for resist underlayer film of this invention, it is preferable that the aromatic ring of the said (a) aromatic ring containing polymer exists in the skeleton part of a polymer. The aromatic ring absorbs radiation having a short wavelength (193 nm, 248 nm) during the lithographic process, thereby minimizing the reflectivity between the backing layers without a separate antireflective coating (ARC) when using the composition of the present invention. On the other hand, the aromatic ring-containing polymer preferably contains a plurality of reactive sites distributed along the polymer reacting with the crosslinking component, for example, hydroxy group (-OH). Therefore, when a crosslinking component such as an alkoxy group (-OCH ₃ ) is included in the composition for resist underlayer film of the present invention, a self-crosslinking reaction occurs, and curing by a baking process is possible without additional crosslinking component. Therefore, when the crosslinking component is additionally included in the composition of the present invention, the curing of the composition may be promoted by an additional crosslinking reaction in addition to the self-crosslinking reaction.

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

In addition, the (b) organic solvent included in the composition of the present invention is not particularly limited as long as it is (a) an organic solvent having sufficient solubility in the aromatic ring-containing polymer, for example, propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monomethyl ether (PGME), cyclohexanone, ethyl lactate and the like can be used.

The composition for resist underlayer film according to the present invention comprises (a) 1 to 25% by weight of an aromatic ring-containing polymer or a mixture thereof, more preferably 3 to 10% by weight and (b) 75 to 99% by weight of an organic solvent. Where possible, the two components are preferably included in the content in the above range to precisely match the desired coating thickness.

In addition, the resist underlayer film composition may further comprise (c) a crosslinking component. The crosslinking component (c) is preferably capable of crosslinking the repeating units of the polymer by heating in a reaction catalyzed by the generated acid.

More specifically, the crosslinking component (c) may be selected from the group consisting of melamine resin, amino resin, glycoluryl compound and bisepoxy compound. More specifically, the crosslinking component is methylated or butylated melamine resin etherified amino resin such as N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin Cymel U-65 Resin or UFR 80 Resin. Methylated or butylated urea resin (Urea Resin) Glycoluril derivative represented by the following formula (9), such as Powderlink 1174, 2,6-bis (hydroxymethyl) -p-cresol compound and the like can be used. In addition, a bisepoxy compound as shown in the following formula (10) can also be used as a crosslinking component.

[Formula 9]

[Formula 10]

The composition for resist underlayer film of this invention can contain additives, such as surfactant, further.

According to yet another embodiment of the present invention, there is provided a method for producing a layer of material, comprising: (a) providing a layer of material on a substrate; (b) forming a resist underlayer film using the composition for resist underlayer film according to the present invention over the material layer; (c) forming a radiation-sensitive imaging layer over the resist underlayer; (d) generating a pattern of radiation-exposed areas within the radiation-sensitive imaging layer by patterning the radiation-sensitive imaging layer to radiation; (e) selectively removing portions of the radiation-sensitive imaging layer and the resist underlayer film to expose portions of the material layer; And (f) etching the exposed portion of the material layer.

The method may further include forming a silicon-containing second underlayer film on the resist underlayer film (first underlayer film) before step (c) of the method of manufacturing a patterned material shape on the substrate.

The method may further include forming a third underlayer film (bottom antireflective layer, BARC) after the forming of the silicon-containing second underlayer film and before the step (c) of the method of manufacturing the patterned material shape on the substrate. can do.

The method of patterning a material on a substrate in accordance with the present invention may be performed more 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 composition for resist underlayer film of the present invention is to be used may be any conductive, semiconductive, magnetic or insulating material.

Subsequently, using the resist underlayer film composition of this invention, a resist underlayer film is formed by spin-coating to the thickness of 500-4000 kPa, and it bakes at 100-500 degreeC for 10 second-10 minutes, and forms a resist underlayer film. At this time, the thickness of the resist underlayer film, baking temperature and time is not limited to the above range can be manufactured in a variety of different forms, those of ordinary skill in the art to which the present invention belongs It will be understood that other specific forms may be practiced without changing the essential features.

When the resist underlayer film is formed, a radiation-sensitive 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 imaging layer. Subsequently, the imaging layer and the antireflective layer are selectively removed to expose portions of the material layer, and dry etching is performed using an etching gas. As a general example of the etching gas may be selected from the group consisting of CHF ₃ , CF ₄ , CH ₄ , Cl ₂ , BCl ₃ and mixtures thereof. After the patterned material shape is formed, any remaining resist can be removed by conventional photoresist strippers.

A semiconductor integrated circuit device can be provided by such a method of manufacturing a patterned material shape on a substrate according to the present invention.

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 conventional semiconductor device 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 isolations), 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, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

In addition, the description is not described herein, so those skilled in the art that can be sufficiently technically inferred the description thereof will be omitted.

Example 1

Synthesis of Aromatic Ring-containing Polymers

[Formula 11]

In a mechanical stirrer, cooling tube, 2 L four-necked flask, 202.3 g (1.0 mol) of pyrene, 106.1 g (1.0 mol) of benzaldehyde and 6.8 g (0.04 mol) of p-toluenesulfonic acid were added to 500 g of propylene glycol monomethyl ether acetate ( The flask was heated in an oil bath with a solution dissolved in PGMEA) and stirred with a magnetic stirrer to raise the temperature of the reaction solution to 100 ° C, and then the reaction was carried out for 12 hours.

After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, and then 5.9 g (0.04 mol) of triethanolamine was added as a neutralizing agent to terminate the reaction. After completion of the reaction, the acid was removed using a water / methanol mixture, followed by methanol to remove the low molecular weight containing the oligomer and monomer, and the aromatic ring-containing polymer represented by Formula 11 (Mw = 10,000, polydispersity = 2.1, n = 34).

Formation of resist underlayer film

0.8 g of the obtained aromatic ring-containing polymer was weighed, dissolved in 9 g of propylene glycol monomethylether acetate (hereinafter referred to as PGMEA), and filtered to prepare a composition for a resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-coating, and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 1500 Pa.

[Example 2]

Synthesis of Aromatic Ring-containing Polymers

[Formula 12]

In a mechanical stirrer, cooling tube, 2 L four-necked flask, 202.3 g (1.0 mol) of pyrene, 156.2 g (1.0 mol) of naphthaldehyde and 6.8 g (0.04 mol) of p-toluenesulfonic acid were added 500 g of propylene glycol monomethyl ether. The flask was heated in an oil bath containing a solution dissolved in acetate (PGMEA) and stirred with a magnetic stirrer to raise the temperature of the reaction solution to 110 ° C., and then reacted for 18 hours.

After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, and then terminated by adding 5.9 g (0.04 mol) of triethanolamine as a neutralizing agent to terminate the reaction. After completion of the reaction, the acid was removed using a water / methanol mixture, and then a low molecular weight containing an oligomer and a monomer and a polymer represented by Chemical Formula 12 (Mw = 10,000, polydispersity = 2.3, n = 29) were removed using methanol. Got it.

Formation of resist underlayer film

0.8 g of the obtained aromatic ring-containing polymer was weighed, dissolved in 9 g of propylene glycol monomethylether acetate (hereinafter referred to as PGMEA), and filtered to prepare a composition for a resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-coating, and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 1500 Pa.

Example 3

Synthesis of Aromatic Ring-containing Polymers

[Formula 13]

202.3 g (1.0 mol) of pyrene, 166.2 g (1 mol) of 1,4-bismethoxymethylbenzene and 6.2 g (0.04 mol) of diethyl sulfate in a mechanical stirrer, cooling tube, 2 L four-necked flask The solution was dissolved in 500 g of propylene glycol monomethyl ether acetate (PGMEA), and the flask was heated in an oil bath stirred with a magnetic stirrer to raise the temperature of the reaction solution to 120 ° C, followed by reaction for 28 hours. It was.

After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, and then terminated by adding 5.9 g (0.04 mol) of triethanolamine as a neutralizing agent to terminate the reaction. After completion of the reaction, the acid was removed using a water / methanol mixture, and then a low molecular weight containing oligomer and monomer and a polymer represented by Chemical Formula 13 (Mw = 6,000, polydispersity = 1.9, n = 20) were added using methanol. Got it.

Formation of resist underlayer film

0.8 g of the obtained aromatic ring-containing polymer was weighed, dissolved in 9 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and filtered to prepare a composition for a resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-coating, and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 1500 Pa.

Example 4

Synthesis of Aromatic Ring-containing Polymers

[Formula 14]

202.3 g (1.0 mol) of pyrene, 266.3 g (1 mol) of 1,4-bismethoxymethylanthracene and 6.2 g (0.04 mol) of diethyl sulfate in a mechanical stirrer, cooling tube, and 2 L four-necked flask ) Was dissolved in 500 g of propylene glycol monomethyl ether acetate (PGMEA), and the flask was heated in an oil bath stirred with a magnetic stirrer to raise the temperature of the reaction solution to 110 ° C. Was carried out.

After completion of the reaction, the reaction vessel was sufficiently cooled to room temperature, and then terminated by adding 5.9 g (0.04 mol) of triethanolamine as a neutralizing agent to terminate the reaction. After completion of the reaction, the acid was removed using a water / methanol mixture, and then, methanol was used to obtain a low molecular weight containing an oligomer and a monomer and a polymer represented by Chemical Formula 14 (Mw = 4,600, polydispersity = 1.7, n = 10). .

Formation of resist underlayer film

0.8 g of the obtained aromatic ring-containing polymer was weighed, poured into 9 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), dissolved, and filtered to prepare a composition for a resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-coating, and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 1500 Pa.

Comparative Example 1

Synthesis of 9,9-bishydroxyphenylfluorene and 1,4-bismethoxymethylbenzene copolymer

[Formula 15]

In a 3 L four-necked flask equipped with a mechanical stirrer and a cooling tube, 350.41 g (1.0 mol) of 9,9-bishydroxyphenylfluorene, 3.08 g (0.02 mol) of diethyl sulfate and propylene glycol monomethyl 350 g of ether was added thereto, followed by stirring while maintaining the temperature of the reactor at 115 ° C. After 10 minutes, 166.22 g (1 mol) of 1,4-bismethoxymethylbenzene was added dropwise, and the reaction was carried out at the same temperature for 15 hours.

To complete the reaction, 2.98 g (0.02 mol) of triethanolamine was added as a neutralizing agent. After completion of the reaction, the acid was removed using a water / methanol mixture, and then a low molecular weight containing oligomer and monomer was removed using methanol to express the polymer represented by Formula 15 (Mw = 10,000, polydispersity = 2.0 n = 17). Got.

Formation of resist underlayer film

0.8 g of the copolymer obtained was weighed, dissolved in 9 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and filtered to prepare a composition for a resist underlayer film.

The resist underlayer film was coated on a silicon wafer by spin-coating, and baked at 300 ° C. for 60 seconds to form a resist underlayer film having a thickness of 1500 Pa.

Refractive index n and extinction coefficient k of the resist underlayer films formed in Examples 1 to 4 and Comparative Example 1 were obtained, respectively. The instrument used was Ellipsometer (J. A. Woollam) and the measurement results are shown in Table 1 below.

In film manufacturing
Sample used Optical properties (193nm) n (refractive index) k (absorption coefficient) Example 1 1.47 0.71 Example 2 1.46 0.50 Example 3 1.49 0.49 Example 4 1.45 0.43 Comparative Example 1 1.43 0.73

As a result of the evaluation, it was confirmed that the composition for a resist underlayer film according to the present invention had a refractive index and an absorbance which can be used as an antireflection film at an ArF (193 nm) wavelength.

[Examples 5 to 8]

The ArF photoresist was coated on each of the resist underlayers prepared in Examples 1 to 4, baked at 110 ° C. for 60 seconds, and exposed using an ArF exposure apparatus ASML1250 (FN70 5.0 active, NA 0.82), followed by tetramethylammonium hydroxide. It was developed with the hydroxide (TMAH, 2.38 wt% aqueous solution). And FE-SEM was used to examine the line and space pattern of 80 nm.

In addition, 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 are considered and recorded in Table 2.

Comparative Example 2

Except for applying the resist underlayer film of Comparative Example 1 in place of the resist underlayer film prepared in Examples 1 to 4, a patterned specimen was prepared in the same process as in Examples 5 to 8, and EL (expose) according to the change in the exposure dose latitude) The margin of focus (DoF) margin according to the distance between the margin and the light source was considered and recorded in Table 2.

In film manufacturing
Sample used Pattern EL margin
(△ mJ / exposure energy mJ) DoF Margin
(Μm) Profile Example 5 4 0.25 cubic Example 6 4 0.25 cubic Example 7 4 0.25 cubic Example 8 4 0.25 cubic Comparative Example 2 4 0.25 cubic

As a result of pattern evaluation, the composition for resist underlayer film which concerns on this invention, and the composition for resist underlayer film which concerns on the comparative example 2 were able to confirm favorable result in a pattern profile and a margin.

[Examples 9 to 12]

Example 5 Each of a patterned specimen to 8 using a CHF ₃ / CF ₄ gas mixture proceeds to dry etching, followed by a CHF ₃ / CF varying the selection ratio of ₄ with a mixed gas was performed by dry etching again. Finally, all remaining organics were removed using O ₂ gas, and then the cross section was examined by FE-SEM, and the results are shown in Table 3 below.

Comparative Example 3

Except for using the patterned specimen in Comparative Example 2 after the etching was carried out in the same manner as in Examples 9 to 12, the cross-section is considered and the results are shown in Table 3 below.

In film manufacturing
Sample used Resist underlayer film
Pattern shape after etching Silicon nitride
Pattern after etching Example 9 Anisotropic Anisotropic Example 10 Anisotropic Anisotropic Example 11 Anisotropic Anisotropic Example 12 Anisotropic Anisotropic Comparative Example 3 Bowing Tapered shape

As a result of the etch evaluation, the composition for resist underlayer film according to the present invention was confirmed that the pattern shape after etching underlayer film etching and after silicon nitride etching was good in each case. This is judged to be satisfactorily performed by etching gas of the resist underlayer film composition of the present invention due to sufficient resistance.

As a result of the etch evaluation, it was confirmed that the composition for resist underlayer film according to Comparative Example 3 was etched bow-shaped isotropically after etching the resist underlayer film, and thus, it was confirmed that a tapered pattern appeared during etching of silicon nitride. This is because the resist underlayer film composition according to Comparative Example 3 under the etch conditions is insufficient in resistance by etching gas, and it is judged that the etching selectivity for etching silicon nitride is insufficient.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (15)

An aromatic ring-containing polymer comprising a repeating unit represented by the following formula (1) and (2). [Formula 1]

(In the formula 1, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2.) [Formula 2]

(In Formula 2, A is a substituted or unsubstituted straight or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of an arylene group, an alkenylene group, and an azo group with one or more -CH ₂ -substituted or unsubstituted groups. Can be.) The method of claim 1, The aromatic ring-containing polymer is an aromatic ring-containing polymer represented by the following formula (3). (3)

(In Chemical Formula 3, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group, A is a substituted or unsubstituted linear or branched alkylene group, wherein said alkylene group is optionally substituted with one or more -CH ₂ -substituted or unsubstituted arylene groups, alkenylene groups and substituents selected from the group consisting of Can be substituted, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2, n is an integer ranging from 2 ≤ n <100.) The method of claim 1, In Chemical Formula 2, A is an aromatic ring-containing polymer selected from the group consisting of compounds represented by the following Chemical Formulas 4 and 5. [Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 4 and 5, A ₁ to A ₃ is a substituted or unsubstituted alkylene group, Ar ₁ is a substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted terphenylene group; Substituted or unsubstituted naphthylene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted pyrene group; Substituted or unsubstituted stilbene group; And it is selected from the group consisting of a substituted or unsubstituted azobenzene group, Ar ₂ is selected from the group consisting of a substituted or unsubstituted phenyl group and a substituted or unsubstituted phenol group, n is 0 or an integer from 1 to 2.) The method of claim 1, The aromatic ring containing polymer has a weight average molecular weight in the range of 2,000 to 10,000 aromatic ring containing polymer. An aromatic ring-containing polymer polymerized from monomers represented by the following formulas (7) and (8). [Formula 7]

(In Chemical Formula 7, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2, X ₁ to X ₄ are the same as or different from each other, and each independently, a hydroxyl group; Aldehyde group; And an alkoxy group, n ₁ to n ₄ are integers from 0 to 2, and n ₁ to n ₄ cannot all be zero.) [Formula 8]

(In Formula 8, A is a substituted or unsubstituted straight or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of an arylene group, an alkenylene group, and an azo group with one or more -CH ₂ -substituted or unsubstituted groups. Can be, X ₅ and X ₆ are the same as or different from each other, and each independently, a hydroxyl group; Aldehyde group; And an alkoxy group, n ₅ to n ₆ are integers from 0 to 2, and n ₅ to n ₆ cannot all be zero.) (a) an aromatic ring-containing polymer comprising a repeating unit represented by the following formula (1) and (2), or a mixture thereof; and (b) organic solvent A composition for resist underlayer film comprising a. [Formula 1]

(In the formula 1, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2.) [Formula 2]

(In Formula 2, A is a substituted or unsubstituted straight or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of an arylene group, an alkenylene group, and an azo group with one or more -CH ₂ -substituted or unsubstituted groups. Can be.) The method of claim 6, The aromatic ring-containing polymer is a composition for a resist underlayer film represented by the following formula (3). (3)

(In Chemical Formula 3, R ₁ to R ₃ are the same as or different from each other, and each independently, hydrogen; Hydroxyl group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; And it is selected from the group consisting of a substituted or unsubstituted heteroaryl group, A is a substituted or unsubstituted straight or branched alkylene group, wherein the alkylene group is optionally substituted with a substituent selected from the group consisting of an arylene group, an alkenylene group, and an azo group with one or more -CH ₂ -substituted or unsubstituted groups. Can be, x is 0 or 1, y is an integer from 0 to 3, z is an integer from 0 to 2, n is an integer ranging from 2 ≤ n <100.) The method of claim 6, In Chemical Formula 2, A is selected from the group consisting of substituents represented by Formulas 4 and 5 below. [Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 4 and 5, A ₁ to A ₃ is a substituted or unsubstituted alkylene group, Ar ₁ is a substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted terphenylene group; Substituted or unsubstituted naphthylene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted pyrene group; Substituted or unsubstituted stilbene group; And it is selected from the group consisting of a substituted or unsubstituted azobenzene group, Ar ₂ is a substituted or unsubstituted phenyl group; And it is selected from the group consisting of a substituted or unsubstituted phenol group, n is 0 or an integer from 1 to 2.) The method of claim 6, The resist underlayer film composition (a) 1 to 25% by weight of an aromatic ring containing polymer or mixtures thereof and (b) 75 to 99% by weight of organic solvent A composition for resist underlayer film comprising a. The method of claim 6, The composition for resist underlayer film, wherein the composition for resist underlayer film further comprises a surfactant. The method of claim 6, The resist underlayer film composition further comprises a crosslinking component. (a) providing a layer of material on the substrate (b) forming a resist underlayer film using the composition for resist underlayer film according to any one of claims 6 to 11 above the material layer. (c) forming a radiation-sensitive imaging layer over the resist underlayer (d) generating a pattern of radiation-exposed areas within the radiation-sensitive imaging layer by patternwise exposing the radiation-sensitive imaging layer to radiation. (e) selectively removing portions of the radiation-sensitive imaging layer and the resist underlayer film to expose portions of the material layer; and (f) etching the exposed portion of the material layer. The method of claim 12, And forming a silicon-containing second underlayer on the resist underlayer (first underlayer) prior to step (c) of the method for producing a patterned material shape on the substrate. Manufacturing method of material shape. The method of claim 13, And forming a third underlayer film (bottom antireflective layer, BARC) after the step of forming the silicon-containing second underlayer film and before step (c) of the method of manufacturing a patterned material shape on a substrate. A method of producing a patterned material shape on a substrate. The method of claim 12, The method of manufacturing a patterned material shape on the substrate is a method of manufacturing a semiconductor integrated circuit device.