KR101333703B1 - Aromatic ring-included polymer for under-layer of resist, under-layer composition of resist including same, and method of patterning device using same - Google Patents

Abstract

상기 화학식에서, 각 치환기는 상세한 설명에서 정의된 바와 같다.An aromatic ring-containing polymer for a resist underlayer film, a resist underlayer film composition comprising the polymer, and a method for forming a pattern of a device, wherein the polymer is an aromatic ring-containing polymer including a unit structure represented by the following general formula (1).
[Chemical Formula 1]

In the above formula, each substituent is as defined in the detailed description.

Description

Aromatic ring-containing polymer for resist underlayer film, resist underlayer film composition comprising the same, and pattern formation method of device using the composition TECHNICAL FIELD PATTERNING DEVICE USING SAME}

The present substrate relates to an aromatic ring-containing polymer for resist underlayer film, a method for producing the polymer, a resist underlayer film composition containing the polymer, and a patterning method for a material using the same.

BACKGROUND OF THE INVENTION In the industrial field, such as the microelectronics industry and micro-scopic structures (e.g., micromachines, magnetoresist heads, etc.), there is a continuing need to reduce the size of structural features. There is also a need in the microelectronics industry to reduce the size of microelectronic devices and to provide a greater amount of circuitry for a given chip size.

Effective lithographic techniques are essential to reduce this feature size.

In a typical lithographic process, first, a resist is applied to a lower layer material, and then exposed to radiation to form a resist layer. The resist layer is then developed with a developer to form a patterned resist layer, and the material in the openings of the patterned resist layer is etched to transfer the pattern to the underlying material. After the transfer is completed, the remaining resist layer is removed.

However, the resist may not have sufficient resistance to the etching step to such an extent that a predetermined pattern can be effectively transferred to the underlying material. Therefore, when an ultra-thin resist layer using an extremely thin resist material is required, when a substrate to be etched is thick, and when a deep etching depth is required, it is necessary to use a specific etchant for a predetermined lower layer material A resist underlayer film has been used.

The resist underlayer film serves as an intermediate layer between the resist layer and the substrate to be patterned, and serves to transfer the pattern of the patterned resist layer to the underlayer material, and thus must withstand the etching process required to transfer the pattern.

Many materials have been tried to form these undercoat films, but there is a continuing need for improved undercoat compositions.

Materials for forming conventional underlayer films are difficult to apply to substrates, for example using chemical or physical vapor deposition, special solvents, and / or high temperature firing, but these are expensive problems. Therefore, in recent years, studies on underlayer film compositions that can be applied by spin-coating without the need for high temperature baking have been conducted. In addition, it can be easily etched selectively using a resist layer formed on the upper side as a mask, and at the same time, when the lower layer is a metal layer, the lower layer film composition resistant to the etching process required for patterning the lower layer using the lower layer film as a mask. Research is ongoing.

In addition, studies on underlayer film compositions that provide adequate shelf life and avoid interfering interactions with the resist layer (e.g., contaminating the resist or substrate by an acid catalyst included in the underlayer film composition) In addition, further research is underway on the underlayer film composition having predetermined optical properties for radiation of shorter wavelengths (eg, 157, 193, 248 nm).

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

One embodiment of the present invention provides an aromatic ring-containing polymer for a resist underlayer film having excellent optical properties, mechanical properties, and etch selectivity properties, which can be applied using a spin-on application technique. It is.

Another embodiment of the present invention is to provide a resist underlayer film composition having little contamination problem due to the use of an acid catalyst.

Another embodiment of the present invention to provide a method of forming a pattern of the device using the resist underlayer film composition.

One embodiment of the present invention to provide an aromatic ring-containing polymer comprising a unit structure represented by the following formula (1).

[Formula 1]

(In the formula 1,

R1 and R2 are independently of each other hydrogen; An alkyl group having 1 to 10 carbon atoms; Or an aromatic group,

A is a functional group derived from an aromatic compound with or without a hetero atom,

n is an integer of 1 or more.)

The weight average molecular weight of the aromatic ring-containing polymer may be 2,000 to 20,000.

The aromatic group may be an aromatic group having 5 to 20 carbon atoms.

In addition, the hetero atom may be N, O, S or P.

Another embodiment of the present invention (a) an aromatic ring-containing polymer comprising a unit structure represented by the formula (1); And (b) to provide a composition for a resist underlayer film containing an organic solvent.

Another embodiment of the invention comprises the steps of (a) providing a layer of material on a substrate; (b) forming a lower layer film on the material layer using the resist lower layer film composition; (c) forming a resist layer on the lower layer film; (d) exposing the substrate on which the resist layer is formed; (e) developing the exposed substrate; And (f) etching the developed substrate.

In the above manufacturing method (c), a step of forming a silicon-containing resist underlayer film before the step of forming a resist layer may be further performed.

In addition, a step of forming a bottom anti-reflective coating (BARC) may be further performed before the forming of the (c) resist layer.

The polymer for resist underlayer film according to one embodiment of the present invention has very excellent optical properties, mechanical properties and etching selectivity properties. In addition, the resist underlayer film composition including the polymer may be applied to a substrate using a spin-on coating technique, is useful for shorter wavelength lithographic processes, and a small amount of an acid catalyst may be used. Can be suppressed.

In addition, the resist underlayer film composition may minimize reflectivity between the resist and the back layer by having a refractive index and absorbance in a useful range as an antireflection film in a deep UV (DUV) region such as an ArF (193 nm) wavelength region when forming a film. Thus, it is possible to provide a lithographic structure having excellent pattern evaluation results in terms of pattern profile and margin. In addition, when performing lithographic technology, the etching selectivity is very high compared to the existing materials, and the resistance profile for the multiple etching is sufficient, so that the etching profile of the resist underlayer film, which is an image to be transferred to the lower layer, is very good.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

According to one embodiment of the present invention, an aromatic ring-containing polymer including a unit structure represented by the following Chemical Formula 1 is provided. The aromatic ring-containing polymer including the unit structure represented by Formula 1 includes an aromatic ring having strong absorption in a short wavelength region (particularly, 193 nm and 248 nm) in the skeleton portion of the polymer and thus used as an antireflection film. It is possible.

[Formula 1]

In Formula 1,

R1 and R2 are independently of each other hydrogen, an alkyl group having 1 to 10 carbon atoms or an aromatic group,

A is a functional group derived from an aromatic compound with or without a hetero atom,

n is an integer of 1 or more. In addition, n may be an integer of 1 to 100.

The aromatic group may be an aromatic group having 5 to 20 carbon atoms, and may be an aromatic group having 6 to 20 carbon atoms.

The hetero atom means N, O, S, or P.

In addition, the functional group derived from the aromatic compound containing or not containing the hetero atom A is a functional group derived from an aromatic compound having 6 to 40 carbon atoms. Specific examples of A may include a functional group derived from an aromatic compound represented by the following Chemical Formula 1a or 1b. In Chemical Formulas 1a and 1b, X * means a site and a terminal site which bind to Si in A of Chemical Formula 1 above. In Formulas 1a and 1b, the alkoxy group may be an alkoxy group of C 1 -C 10.

[Formula 1a]

(In the formula (1a)

R3 and R4 are independently of each other hydrogen, a hydroxy group, an alkoxy group or a lower alkyl group of C1-C4,

R5 and R6 are each independently of the other hydrogen, alkoxy group, C1-C4 lower alkyl group or hydroxy group,

X is O (oxygen) or S (sulfur) and may be O.)

[Chemical Formula 1b]

(In the above formula (1b)

R7 and R8 are independently of each other hydrogen, alkoxy group, hydroxy group or C1-C4 lower alkyl group,

R9 and R10 are each independently hydrogen, alkoxy group, C1-C4 lower alkyl group or hydroxy group,

X is O (oxygen) or S (sulfur), specifically O (oxygen).)

Specific examples of the aromatic compound include 9,9'-bisphenolfluorene, 9,9-bis (1-naphthol) fluorene, 9,9-bis (1-naphthol) fluorene, Dihydroxy benzene, dihydroxy naphthalene, dihydroxy pyrene, dihydroxy anthracene or combinations thereof, but is not limited to these compounds.

The weight average molecular weight of the aromatic ring-containing polymer may be 2,000 to 20,000. When the weight average molecular weight of the aromatic ring-containing polymer is included in the above range, the desired coating thickness can be realized or a good thin film can be formed.

The underlayer film prepared using the aromatic ring-containing polymer may have an absorbance of 0.3 to 0.7, and having such absorbance may function as an antireflection film.

The aromatic ring-containing polymer according to one embodiment of the present invention may be prepared by reacting an aromatic compound capable of inducing A and a dichlorosilane compound represented by the following Chemical Formula 5 in a solvent with a weak base in the following Chemical Formula 1. Of course, the method for preparing the aromatic ring-containing polymer according to one embodiment of the present invention is not limited to this method, and of course, it can be prepared by other methods.

[Chemical Formula 5]

In Formula 5, R1 and R2 are the same as defined in Formula 1.

Specific examples of the aromatic compound capable of inducing A include 9,9'-bisphenolfluorene and 9,9-bis (1-naphthol) fluorene (9,9-bis (1). -naphthol) fluorene), dihydroxy benzene, dihydroxy naphthalene, dihydroxy pyrene, dihydroxy anthracene or combinations thereof, but is not limited to these compounds.

More specific examples of the aromatic compound capable of inducing A include compounds represented by the following Chemical Formulas 1a 'and 1b'.

[Chemical Formula 1a ']

(In Formula 1a ', R3 to R6 are the same as in Formula 1a, and Y is -OH or -SH.)

[Formula 1b ']

(In Formula 1b ', R7 to R10 are the same as in Formula 1b, and Y is -OH or -SH.)

Examples of the weak base include triethylamine, aniline, pyridine, aluminum hydroxide, and the like, but are not limited thereto.

As the solvent, any organic solvent may be used, and any of those capable of dissolving the aromatic compound, dichlorosilane compound, and weak base may be used. Specific examples of the solvent may include toluene, xylene, and the like, but are not limited thereto.

The aromatic compound, the dichlorosilane compound and the weak base may be dissolved in a solvent and reacted at a temperature of −20 to 100 ° C. for 5 to 15 hours to prepare an aromatic ring-containing polymer according to one embodiment of the present invention. At this time, the mixing ratio of the aromatic compound and the dichlorosilane compound can be appropriately adjusted, and of course, conditions such as temperature can also be appropriately adjusted.

Another embodiment of the present invention relates to a resist underlayer film composition comprising (a) an aromatic ring-containing polymer and (b) an organic solvent.

It will not specifically limit, if it is an organic solvent which has sufficient solubility with respect to the said polymer as said organic solvent. However, representative examples of organic solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate. lactate), gamma-butyrolactone (GBL), acetyl acetone, and the like.

In the resist underlayer film composition according to the embodiment of the present invention, the content of the aromatic ring-containing polymer may be 1 to 20% by weight, or 3 to 10% by weight. When the content of the aromatic ring-containing polymer is included in the above range, the composition can be appropriately adjusted to the desired coating thickness when forming the resist underlayer film.

In addition, the content of the organic solvent may be the remainder, that is, 80 to 99% by weight, and when the content of the organic solvent is included in the above range, the desired coating thickness is applied to the desired coating thickness when applying the composition to form a resist underlayer film. I can regulate it.

The resist underlayer film composition according to the embodiment of the present invention may further include a surfactant or may further include a crosslinking component. It may also further comprise an acid catalyst.

In this case, the content of the surfactant may be 0.01 to 1 parts by weight based on 100 parts by weight of the resist underlayer film composition, and the content of the crosslinking component may be 0.01 to 1 parts by weight based on 100 parts by weight of the resist underlayer film composition. In addition, the content of the acid catalyst may be 0.01 to 1 parts by weight based on 100 parts by weight of the resist underlayer film composition.

When the content of the crosslinking component is within the above range, appropriate crosslinking properties can be obtained without changing the optical properties of the lower layer film to be formed.

Examples of the surfactant include, but are not limited to, alkylbenzenesulfonates, alkylpyridinium salts, polyethylene glycols, and quaternary ammonium salts.

The crosslinking component is not particularly limited as long as it is a crosslinking agent capable of crosslinking the repeating units of the polymer in a manner that can be catalyzed by an acid. Representative examples of the crosslinking component may include melamine resins, amino resins, glycoluril compounds, bisepoxy compounds, or mixtures thereof.

Specific examples of the crosslinking component include etherified amino resins such as methylated or butylated melamine resins (specific examples being N-methoxymethyl-melamine resin or N-butoxymethyl-melamine resin) and methylation. Or butylated urea resins (specific examples are Cymel U-65 Resin or UFR 80 Resin), glycoluril derivatives represented by the formula (30) (specific examples are Powderlink 1174), 2,6-bis (hydr Oxymethyl) -p-cresol compound). In addition, bisepoxy-based compounds represented by the following formula (31) and melamine derivatives represented by the following formula (32) can also be used as crosslinking components.

(30)

(31)

(32)

As the acid catalyst, an organic acid such as p-toluene sulfonic acid monohydrate may be used, and a compound of a thermal acid generator system having a storage stability may be used as a catalyst. . Thermal acid generators are acid generator compounds which are intended to release acids upon thermal treatment, for example pyridinium p-tolene sulfonate, 2,4,4,6-tetrabromocyclohexadiene Preference is given to using on, benzointosylate, 2-nitrobenzyltosylate, alkyl esters of euphonic acid, and the like. 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.

Another embodiment of the present invention provides a method of forming a pattern of a device using a resist underlayer film composition, comprising the steps of: (a) providing a material layer on a substrate; (b) forming a resist underlayer film on the material layer using the resist underlayer film composition; (c) forming a resist layer on the resist underlayer film layer; (d) exposing the substrate on which the resist layer is formed; (e) developing the exposed substrate; And (f) etching the developed substrate.

Hereinafter, this pattern forming method will be described in detail.

First, a material layer is formed on a substrate.

As the substrate, a silicon substrate may be used, and any of materials constituting the material layer may be any of conductive, semi-conductive, magnetic or insulating materials. Typical examples thereof include aluminum, SiN (silicon nitride) have. Since the method of forming the material layer is a conventional method, a detailed description thereof will be omitted here.

Subsequently, the resist underlayer film is formed using the resist underlayer film composition according to the embodiment of the present invention. The resist underlayer film forming process may be formed by coating the resist underlayer film composition at a thickness of 500 to 4000 kPa and baking. The coating process may be performed by a spin coating process, and the baking process may be performed at 100 to 500 ° C. for 10 seconds to 10 minutes. The coating process, the thickness of the lower layer film, the baking temperature and the time are not limited to the above range, but can be manufactured in various forms, and those skilled in the art will understand that the technical idea of the present invention It is to be understood that the invention may be embodied in other specific forms without departing from the essential characteristics thereof.

When the resist underlayer film is formed, a resist layer (photosensitive imaging layer) is formed on the resist underlayer film. Since the resist layer can be formed by a generally known process of applying and baking a photosensitive resist composition, a detailed description thereof will be omitted herein.

The step of forming the silicon-containing resist lower layer film before forming the resist layer may be further performed, or the step of forming the antireflection layer may be further performed. It is needless to say that the steps of forming the silicon-containing resist lower layer film and then forming the antireflection layer may all be performed. The formation of the silicon-containing resist lower layer film and the antireflection layer are well known in the art, so a detailed description thereof will be omitted herein.

The resist layer is then exposed. This exposure process is performed using various exposure sources such as ArF or EUV (Extreme UV), E-beam, or the like. When the exposure is completed, a baking process is performed so that a chemical reaction occurs in the exposure area. This baking process may be carried out for about 60 to 90 seconds in the temperature range of about 90 to 120 ℃.

Then, a development process is performed. The developing step may be carried out with a basic aqueous solution. As the basic aqueous solution developer, an aqueous solution of tetramethylammonium hydroxide (TMAH) may be used. When the used exposure source is an ArF excimer laser, a line and space pattern of 80 to 100 nm can be formed at a dose of about 5 to 30 mJ / cm 2.

According to the developing process, the resist layer and the resist undercoat film are selectively removed to expose a part of the material layer.

Then, an etching process is performed. According to this etching process, the exposed material layer is etched to form a pattern. The etching process may include an etching gas such as halogen gas; Or a plasma such as a fluorocarbon gas such as CHF ₃ or CF ₄ . Then, a desired pattern can be formed by removing a resist layer, a resist underlayer film, and the like remaining on the substrate by using a stripper.

According to this process, 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 according to conventional semiconductor device manufacturing 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 should also be understood that the invention is not limited to any particular lithographic technique or device structure.

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

Synthesis Example 1

In a reactor equipped with a mechanical stirrer, a cooling tube, and a 10 L flask, 350.4 g (1.0 mol) of 9,9'-bisphenolfluorene, 191.1 g (1.0 mol) of phenyl methyl dichlorosilane and 202.4 g (2.0 mol) of triethylamine were added. It melt | dissolved in 3500 g of toluene, stirred this solution with the stirrer, reaction was performed at 60 degreeC for 10 hours, and reaction was complete | finished.

After completion of the reaction, triethylamine hydrochloride was removed using water, and the toluene solvent was distilled under reduced pressure to obtain a polymer represented by the following Chemical Formula 2 (Mw = 4,300, molecular weight distribution (polydispersity) = 1.6, n = 8).

(2)

Synthesis Example 2

In a reactor equipped with a mechanical stirrer, a cooling tube, and a 10 L flask, 350.4 g (1.0 mol) of 9,9'-bisphenolfluorene, 253.2 g (1.0 mol) of diphenyl dichlorosilane, and 202.4 g (2.0 mol) of triethylamine were added. After dissolving in 3500 g of toluene, this solution was stirred with the stirrer and reaction was complete at 60 degreeC for 10 hours, and reaction was complete | finished.

After completion of the reaction, triethylamine hydrochloride was removed using water, and the toluene solvent was distilled under reduced pressure to obtain a polymer represented by Chemical Formula 3 (Mw = 3,600, molecular weight distribution (polydispersity) = 1.4, n = 6).

(3)

Synthesis Example 3

450.5 g (1.0 mol) of 9,9-bis (1-naphthol) fluorene, 129.1 g (1.0 mol) of dimethyl dichlorosilane and 202.4 g of triethylamine in a reactor equipped with a mechanical stirrer, a cooling tube and a 10 L flask (2.0 mol) was dissolved in 4000 g of toluene, the solution was stirred with a stirrer, and the reaction was terminated after performing the reaction at 60 ° C for 12 hours.

After completion of the reaction, triethylamine hydrochloride was removed using water, and the toluene solvent was distilled under reduced pressure to obtain a polymer represented by the following formula (Mw = 5,700, molecular weight distribution (polydispersity) = 1.7, n = 10).

[Formula 4]

Synthesis Example 4

450.5 g (1.0 mol) of 9,9-bis (1-naphthol) fluorene, 253.2 g (1.0 mol) of diphenyl dichlorosilane and 202.4 g of triethylamine in a reactor equipped with a mechanical stirrer, a cooling tube and a 10 L flask 2.0 mol) was dissolved in 4000 g of toluene, the solution was stirred with a stirrer, and the reaction was terminated after performing the reaction at 60 ° C for 12 hours.

After completion of the reaction, triethylamine hydrochloride was removed using water, and the toluene solvent was distilled off under reduced pressure to obtain a polymer represented by Chemical Formula 5 (Mw = 5,600, molecular weight distribution (polydispersity) = 1.4, n = 8).

[Chemical Formula 5]

Synthesis Example 5

450.5 g (1.0 mol) of 9,9-bis (1-naphthol) fluorene, 283.4 g (1.0 mol) of dichloro dodecyl methyl silane and 202.4 g of triethylamine in a reactor equipped with a mechanical stirrer, a cooling tube and a 10 L flask (2.0 mol) was dissolved in 4000 g of toluene, the solution was stirred with a stirrer, and the reaction was terminated after the reaction was performed at 60 ° C. for 12 hours.

After completion of the reaction, triethylamine hydrochloride was removed using water, and the toluene solvent was distilled under reduced pressure to obtain a polymer represented by the following formula (Mw = 5,200, molecular weight distribution (polydispersity) = 1.5, n = 7).

[Chemical Formula 6]

[Examples 1 to 3]

0.8 g of each of the polymers prepared in Synthesis Examples 1 to 4 was weighed and dissolved in 9 g of propylene glycol monomethylether acetate (hereinafter referred to as PGMEA), followed by filtration. A resist underlayer film composition was made.

The resist underlayer film composition prepared in Examples 1 to 4 was coated on a silicon wafer by spin-coating, and baked at 400 ° C. for 60 seconds to form a resist underlayer film having a thickness of 2500 Pa.

The refractive index n and the absorbance k of the underlayer film were measured. The instrument used was measured using an Ellipsometer (JA Woollam) instrument. The measurement results are shown in Table 1 below.

Comparative Example 1

A resist underlayer film was formed in the same manner as in Examples 1 to 4 except that the polymer of Synthesis Example 5 was applied instead of the polymer of Synthesis Examples 1 to 4. The n and k values of the formed underlayer films were obtained, respectively, and shown in Table 1 below.

Polymers Used to Prepare Underlayer Membranes Optical properties (193 nm) n (refractive index) k (absorbance) Example 1 1.41 0.40 Example 2 1.39 0.66 Example 3 1.33 0.38 Example 4 1.42 0.61 Comparative Example 1 1.43 0.73

As shown in Table 1, the evaluation results confirmed that the compositions of Examples 1 to 4 at the ArF (193 nm) wavelength has a refractive index and absorbance that can be used as an antireflection film.

[Examples 5 to 8]

The resist underlayer film compositions prepared in Examples 1 to 4 were each coated by spin-coating on a silicon wafer coated with SiN (silicon nitride), and baked at 400 ° C. for 60 seconds to form an underlayer film having a thickness of 2500 Pa.

Subsequently, an ArF photoresist was coated on the underlayer film and baked at 110 ° C. for 60 seconds. After the baking process was completed, it was exposed using an ArF exposure equipment ASML1250 (FN70 5.0 active, NA 0.82) and then developed with tetramethylammonium hydroxide (2.38 wt% concentration aqueous solution). In addition, the line and space pattern of 80 nm was examined using FE (Field Emission) -SEM.

The exposure latitude (EL) margin according to the change of the exposure amount and the depth of focus (DoF) margin according to the distance change between the light source were measured, and the results are shown in Table 2 below.

Comparative Example 2

Except for using the resist underlayer film composition of Comparative Example 1 in place of the resist underlayer film composition of Examples 1 to 4 to prepare a patterned specimen in the same manner as in Examples 5 to 8 to produce the EL, DoF, pattern profile of the pattern Were obtained respectively. The results are shown in Table 2 below.

To manufacture underlayer film
Samples used Pattern EL margin
(△ mJ / exposure energy mJ) DoF margin
(탆) 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 shown in Table 2 above, in terms of pattern evaluation, EL margin, DoF margin, and pattern profile, good results without significant differences were found in comparison with Examples.

[Examples 9 to 12]

The patterned specimens in Examples 5 to 8 CHF ₃ and CF _4, using a mixed gas, and proceed with the dry etching of the lower layer film, followed by a CHF ₃ and CF varying the selection ratio of _4, using a gas mixture Silicon Nitride Dry etching on the ride was carried out 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 prepared in Comparative Example 2 after the etching in the same manner as in Examples 9 to 12 after considering the cross-section is shown in Table 3 below.

After etching the lower layer
Pattern shape 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 etching evaluation, as shown in Table 3, the lower layer films of Examples 9 to 12 formed of the lower layer film compositions of Examples 1 to 4 have good pattern patterns after the lower layer film etching and after the silicon nitride etching in each case. It is judged that the etching of silicon nitride was performed well because the resistance by the etching gas was sufficient.

In contrast, in the lower layer film of Comparative Example 3 formed of the lower layer film composition of Comparative Example 1, after the lower layer film etching, the bow-shaped isotropic etching aspect was confirmed, and thus, it was judged that the tapered aspect appeared during etching of silicon nitride.

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 (14)

An aromatic ring-containing polymer for a resist underlayer film containing a unit structure represented by the following formula (1).
[Formula 1]

(In Formula 1,
R1 and R2 are independently of each other hydrogen; An alkyl group having 1 to 10 carbon atoms; Or an aromatic group,
A is a functional group derived from an aromatic ring containing compound represented by the formula of any one of formulas 1a and 1b,
n is an integer of 1 or more.)
[Formula 1a]

(In the formula (1a)
R3 and R4 are independently of each other hydrogen, a hydroxy group, a C1-C4 lower alkyl group or an alkoxy group,
R5 and R6 are independently of each other hydrogen, a hydroxy group, a C1-C4 lower alkyl group or an alkoxy group,
X is O (oxygen) or S (sulfur).)
[Chemical Formula 1b]

(In the above formula (1b)
R7 and R8 are independently of each other hydrogen, a hydroxy group, an alkoxy group or a lower alkyl group of C1-C4,
R9 and R10 are independently of each other hydrogen, a hydroxy group, a C1-C4 lower alkyl group or an alkoxy group,
X is O (oxygen) or S (sulfur).)
delete The method of claim 1,
The aromatic group-containing polymer for resist underlayer film, wherein the aromatic group is an aromatic group having 5 to 20 carbon atoms.
delete The method of claim 1,
The aromatic ring-containing polymer is an aromatic ring-containing polymer for a resist underlayer film having a weight average molecular weight of 2,000 to 20,000.
The method of claim 1,
N is an aromatic ring-containing polymer for a resist underlayer film, wherein the integer is from 1 to 100.
(a) an aromatic ring-containing polymer for resist underlayer film according to claim 1; And
(b) organic solvent
A resist underlayer film composition comprising a.
The method of claim 7, wherein
The content of the (a) aromatic ring-containing polymer is 1 to 20% by weight, the content of the organic solvent (b) is 80 to 99% by weight of the resist underlayer film composition.
The method of claim 7, wherein
Wherein the resist underlayer film composition further comprises a surfactant.
The method of claim 7, wherein
Wherein the resist underlayer film composition further comprises a crosslinking component.
(a) forming a layer of material on a substrate;
(b) forming a resist underlayer film on the material layer using the resist underlayer film composition according to any one of claims 7 to 10;
(c) forming a resist layer on the underlayer film;
(d) exposing the substrate on which the resist layer is formed;
(e) developing the exposed substrate; And
(f) etching the developed substrate
And patterning the device.
12. The method of claim 11,
And (c) forming a silicon-containing resist underlayer film prior to forming the resist layer.
The method of claim 12,
And forming an anti-reflective layer after forming the silicon-containing resist underlayer film but prior to (c) forming the resist layer.
The method of claim 13,
And the method of patterning the material is a method of manufacturing a semiconductor integrated circuit device.