WO2013100411A1 - Cyanuric acid derivative, resist underlayer composition comprising the cyanuric acid derivative, and pattern forming method using the resist underlayer composition - Google Patents

Abstract

The present invention relates to: a cyanuric acid derivative expressed by chemical formula 1; a resist underlayer composition comprising the cyanuric acid derivative; and a pattern forming method using the composition.

Description

Cyanuric acid derivative, composition for resist underlayer film containing said cyanuric acid derivative, and pattern formation method using the composition for resist underlayer film

The present invention relates to a cyanuric acid derivative, a composition for resist underlayer film containing the cyanuric acid derivative, and a pattern formation method using the composition for resist underlayer film.

There is a need to reduce the size of patterns to provide larger amounts of circuitry for a given chip size, as well as in microelectronics as well as in the fabrication of microscopic structures (eg, micromachines, magnetoresist heads, etc.). .

Effective lithographic techniques are necessary to reduce the pattern size. Lithographic influences the fabrication of microscopic structures in terms of directly imaging a pattern on a given substrate, as well as in manufacturing a mask typically used for such imaging.

Typical lithographic processes include forming a patterned resist layer by patterning exposing the radiation-sensitive resist to imaging radiation. The exposed resist layer is then developed with a 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.

However, 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 layer behind the resist.

Thus, for example, when an ultra thin resist layer is required, when the backing material to be etched is thick, when a considerable etching depth is required and / or when a specific etching solution is required for a given backing material, so-called resist underlayer film Called 　 The layer is used as an intermediate layer between the resist layer and a layer of material that can be patterned by transfer from the patterned resist.

The resist underlayer film may be formed using a composition for resist underlayer film having high etching selectivity, sufficient resistance to multiple etching, and minimizing reflection between the resist layer and the material layer.

The resist underlayer film composition is important for determining the exposure characteristics such as resolution, lithography speed and residue of the resist layer. This exposure characteristic is particularly important when performing ultrafine lithography processes using extreme ultraviolet radiation (EUV) lasers.

One embodiment provides a cyanuric acid derivative for use in a resist underlayer film.

Another embodiment provides a composition for a resist underlayer film including the cyanuric acid derivative.

Another embodiment provides a pattern formation method using the photoresist underlayer film composition.

According to one embodiment, a cyanuric acid derivative represented by Chemical Formula 1 is provided.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted or unsubstituted C7 to C20 arylalkylene group, substituted or unsubstituted C1 to C20 heteroalkylene group, substituted or unsubstituted C2 to C30 heterocycloalkylene group, substituted or unsubstituted C2 to C30 heteroarylene group, substituted or unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof.

In Formula 1, at least one of R ¹ to R ³ may be a heterocycloalkyl group or a heteroaryl group including at least one of nitrogen (N), sulfur (S), oxygen (O), and phosphorus (P).

In Formula 1, at least one of R ¹ to R ³ may be selected from the following Formula a, Formula b, or a combination thereof.

[Formula a]

[Formula b]

In Chemical Formula a or Chemical Formula b,

R ⁴ to R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

* Indicates a linking moiety to sulfur (S) of the formula (1).

The cyanuric acid derivative may be represented by at least one of Chemical Formula 1a and Chemical Formula 1b.

[Formula 1a]

[Formula 1b]

According to another embodiment, the composition for resist underlayer film containing the cyanuric acid derivative mentioned above, the photosensitive polymer, and a solvent is provided.

The cyanuric acid derivative and the photosensitive polymer are based on 100 parts by weight of the solvent. 　 each 　 About 0.1 to 5 parts by weight and about 0.1 to 30 parts by weight.

According to another embodiment, the step of providing a material layer on a substrate, applying the above-described composition for a resist underlayer film on the material layer, heat-treating the composition for a resist underlayer film to form a resist underlayer film, the resist underlayer film Forming a resist layer thereon; exposing and developing the resist layer to form a resist pattern; selectively removing the resist underlayer film using the resist pattern and exposing a portion of the material layer; and the material It provides a pattern forming method comprising etching the exposed portion of the layer.

The forming of the resist underlayer film may be performed by a spin-on coating method.

Film density, solvent elution and exposure characteristics can be improved.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl or I), hydroxy group, alkoxy group, nitro group, cyano group, amino group, azido group, amidino Groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, and C2 to C2 C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C4 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, C6 to Substituted with a substituent selected from C15 cycloalkynyl group, C2 to C20 heterocycloalkyl group and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.

Cyanuric acid derivatives according to one embodiment may be represented by the formula (1).

[Formula 1]

In Chemical Formula 1,

R ¹ to R ³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof to be.

At least one of R ¹ to R ³ may be a heterocycloalkyl group or a heteroaryl group including at least one of nitrogen (N), sulfur (S), oxygen (O), and phosphorus (P).

For example, at least one of R ¹ to R ³ may be selected from the following Chemical Formula a, Chemical Formula b, or a combination thereof.

[Formula a]

[Formula b]

In Chemical Formula a or Chemical Formula b,

R ⁴ to R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

* Indicates a linking moiety to sulfur (S) of the formula (1).

As such, by introducing a heterocycloalkyl group or a heteroaryl group containing at least one of nitrogen (N), sulfur (S), oxygen (O), and phosphorus (P) to the cyanuric acid derivative, the film density of the resist underlayer film is increased and etched. You can speed it up.

L ¹ to L ⁶ are each a linking group, each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, substituted Or an unsubstituted C3 to C30 cycloalkenylene group, a substituted or unsubstituted C7 to C20 arylalkylene group, a substituted or unsubstituted C1 to C20 heteroalkylene group, a substituted or unsubstituted C2 to C30 heterocycloalkylene group, substituted Or an unsubstituted C2 to C30 heteroarylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof.

The composition for a resist underlayer film according to another embodiment includes a cyanuric acid derivative, a photosensitive polymer, and a solvent described above.

The photosensitive polymer is not particularly limited as long as it is a compound that causes a chemical reaction by light, and examples thereof include (meth) acrylic polymers, ester polymers, styrene polymers, novolac polymers, and blended polymers thereof.

The photosensitive polymer may have a weight average molecular weight of about 2,000 kPa to 100,000 kPa, of which about 4,000 kPa to 15,000 kPa. When the weight average molecular weight of the said photosensitive polymer is the said range, solubility to the said solvent improves.

As described above, in the present embodiment, the cyanuric acid derivative and the photosensitive polymer are each included as one component of the composition for the resist underlayer film, and the cyanuric acid derivative and the photosensitive derivative are not included in the form of a polymer chemically bonded. When the cyanuric acid derivative is in the form of a single molecule, it is easy to control the molecular weight, and when the crosslinking reaction occurs with the photosensitive polymer in the form of a single molecule, the crosslinking reaction may proceed uniformly as a whole.

The solvent is not particularly limited as long as it has sufficient solubility or dispersibility in the cyanuric acid derivative and the photosensitive polymer, and for example, propylene glycol, propylene glycol diacetate, methoxy propanediol, diethylene glycol, diethylene glycol butyl ether At least one selected from tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone (or anon), ethyl lactate, gamma-butyrolactone, and acetylacetone can do.

The cyanuric acid derivative may be included in an amount of about 0.1 kPa to 5 kPa with respect to 100 parts by weight of the solvent. Within the above range, the cyanuric acid derivative may be included in an amount of about 0.25 kPa to 2.5 kPa by weight based on 100 parts by weight of the solvent. Since the cyanuric acid derivative is included in the above range, unnecessary particles are not formed during spin-on coating, and crosslinking force with the photosensitive polymer is optimized.

The photosensitive polymer may be included in an amount of about 0.1 to 30 parts by weight based on 100 parts by weight of the solvent. Within this range, the photosensitive polymer is based on 100 parts by weight of the solvent. 　 It is preferably included in about 0.5 to 10 parts by weight. Since the photosensitive polymer is included in the above range, the thickness of the resist underlayer film can be well controlled to a target thickness.

The photoresist composition for the resist underlayer film may increase the film density by including the cyanuric acid derivative, thereby preventing the inflow of contaminants from the substrate or the lower film. In addition, by adjusting the polarity of the composition for the resist underlayer film by the cyanuric acid derivative to reduce the resist residues remaining on the resist underlayer film after the exposure and / or development process to reduce the resolution, line-width roughness ( line-width roughness (LWR) and developing residuals can be improved.

The photoresist underlayer film composition may further include at least one additive selected from a surfactant, an acid catalyst, a crosslinking agent, and the like.

The surfactant may be, for example, alkylbenzenesulfonic acid salt, alkylpyridinium salt, polyethylene glycol, quaternary ammonium salt and the like, but is not limited thereto.

The acid catalyst is preferably a heat activated acid catalyst.

As the acid catalyst, an organic acid such as p-toluene sulfonic acid monohydrate may be used, and a thermal acid generator (TAG) having storage stability may be used. Thermal acid generators are acid generators that release acids upon heat treatment, such as pyridinium p-toluene sulfonate, 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyl Tosylate, alkyl esters of euphonic acid, and the like.

The crosslinking agent may crosslink the repeating unit of the polymer by heating, and may include an amino resin such as an etherified amino resin; Glycoluril compounds such as compounds represented by the following formula (A); Bisepoxy compounds, such as a compound represented by following formula (B); Melamine or derivatives thereof such as N-methoxymethyl melamine, N-butoxymethyl melamine or melamine derivatives represented by the following general formula (C); Or mixtures thereof.

[Formula A]

[Formula B]

[Formula C]

The surfactant, the acid catalyst and the crosslinking agent may be included in an amount of about 0.001 to 3 parts by weight based on 100 parts by weight of the composition for the resist underlayer film. By including in the said range, solubility and crosslinkability can be ensured without changing the optical characteristic of a resist underlayer film.

The resist underlayer film composition may not be dissolved in a solvent for resist and / or a developer for forming a resist, and may not be mixed with a resist forming resist solution to be chemically stable during the process.

Hereinafter, the method of forming a pattern using the composition for resist underlayer films mentioned above is demonstrated.

According to one or more exemplary embodiments, a pattern forming method includes: providing a material layer on a substrate, applying a composition for photoresist underlayer film comprising a cyanuric acid derivative, a photosensitive polymer, and a solvent on the material layer, and the composition for a resist underlayer film. Heat-treating to form a resist underlayer film, forming a resist layer on the resist underlayer film, exposing and developing the resist layer to form a resist pattern, and selectively removing the resist underlayer film using the resist pattern. And exposing a portion of the material layer, and etching the exposed portion of the material layer.

The substrate may be, for example, a silicon wafer, a glass substrate or a polymer substrate.

The material layer is a material to be finally patterned, and may be, for example, a metal layer such as aluminum or copper, a semiconductor layer such as silicon, or an insulating layer such as silicon oxide, silicon nitride, or the like. The material layer can be formed, for example, by chemical vapor deposition.

The resist underlayer film coating composition may be prepared in a solution form and applied by a spin-on coating method. At this time, the coating thickness of the resist underlayer film composition is not particularly limited, but may be applied, for example, to a thickness of about 100 kPa to 10,000 kPa.

Exposing the resist layer may be performed using, for example, ArF, KrF or EUV. In addition, the heat treatment may be performed at about 90 to 500 ° C. after exposure.

Etching the exposed portion of the material layer may be performed by dry etching using an etching gas, which may use, for example, CHF ₃ , CF ₄ , Cl ₂ , BCl ₃ and mixtures thereof.

The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied in various patterns in a semiconductor integrated circuit device.

Through the following examples will be described in more detail the embodiment of the present invention. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention.

Synthesis of Cyanuric Acid Derivatives

Synthesis Example 1

3.0 g of tris- (2,3-epoxypropyl) -isocyanurate (a) was dissolved in 40 g of tetrahydrofuran (THF). 5.0637 g of 2-mercaptobenzothiazole (b) and 0.17 g of benzyltriethylammonium chloride were added to the solution, followed by reacting at 70 ° C for 24 hours. After the reaction, the resultant was dissolved in methylene chloride (methylene chloride) and then slowly precipitated in a hexane (n-hexane) solvent, and the resulting precipitate was filtered. The filtered precipitate was then dried in a vacuum oven maintained at 50 ° C. for about 24 hours to obtain a cyanuric acid derivative represented by the following (c).

Scheme 1

Synthesis Example 2

3.0 g of tris- (2,3-epoxypropyl) -isocyanurate (a) was dissolved in 40 g of tetrahydrofuran (THF). 4.5475 g of 2-mercaptobenzimidazole (d) and 0.17 g of benzyltriethylammonium chloride were added to the solution, followed by reacting at 70 ° C for 24 hours. After the reaction was dissolved in methylene chloride and then slowly precipitated in hexane solvent, and the resulting precipitate was filtered. The filtered precipitate was then dried in a vacuum oven maintained at 50 ° C. for about 24 hours to obtain a cyanuric acid derivative represented by (e) below.

Scheme 2

Synthesis of Photosensitive Polymer

Synthesis Example 3

40 mmol of γ-butyrolactonyl methacrylate (GBLMA), 40 mmol of hydroxyisopropyl methacrylate (4-hydroxyphenyl methacrylate), and 4-hydroxyphenyl methacrylate in a flask under nitrogen atmosphere. 20 mmol and methyl ethyl ketone (solvent, about 2 times the total weight of the monomers) were added and mixed. 10 mmol of dimethyl-2,2'-azobis (2-methylpropionate) (V601, manufactured by Wako Chemicals) was added thereto as a polymerization initiator, followed by addition of a syringe for about 4 hours at a temperature of 80 캜, followed by 2 hours. Further polymerized.

After the polymerization was completed, the polymer obtained was slowly precipitated in an excess of hexane solvent, the resulting precipitate was filtered, and the precipitate was dissolved in an appropriate amount of n-hexane / isopropanol (IPA) mixed solvent and stirred. Subsequently, the obtained precipitate was dried for about 24 hours in a vacuum oven maintained at 50 ℃ to obtain a photosensitive polymer represented by the following formula (2).

[Formula 2]

(a = 40, b = 40, c = 20)

The yield was 75%, the weight average molecular weight (Mw) of the obtained photosensitive polymer was 7,903, and dispersion degree (Mw / Mn) was 1.4.

Preparation of resist underlayer film composition

Example 1

0.5 g of the cyanuric acid derivative obtained in Synthesis Example 1, 1.5 g of the photosensitive polymer obtained in Synthesis Example 3, 0.3 g of a glycoluril compound having the structure of Formula A as a crosslinking agent (PD1174, manufactured by TCI) and acid catalyst 0.05 g of pyridinium para-toluenesulfonate (pPTS) having a structure of propylene glycol monomethyl ether acetate (PGMEA) / propylene glycol monomethyl ether (PGME) (7/3 v / v) 100 g After melting, it was filtered to prepare a composition for resist underlayer film.

[PD1174] [pPTS]

Example 2

A composition for a resist underlayer film was prepared in the same manner as in Example 1-1 except that the cyanuric acid derivative obtained in Synthesis Example 2 was used instead of the cyanuric acid derivative obtained in Synthesis Example 1.

Comparative Example 1

A composition for resist underlayer film was prepared in the same manner as in Example 1 except that the cyanuric acid derivative obtained in Synthesis Example 1 was not included.

Formation of resist underlayer film

The compositions according to Examples 1 and 2 and Comparative Example 1 were applied onto the silicon wafer by spin-on coating, and then heat-treated at 205 ° C. for 1 minute on a hot plate to form a resist underlayer film having a thickness of about 100 μs.

Evaluation-1: Membrane Density

The density of the resist underlayer film formed from the composition according to Examples 1 and 2 and Comparative Example 1 was measured. 　 The density of the underlayer film was measured using an X-Ray Diffractometer (Model: X'Pert PRO MPD, manufactured by Panalytical (Netherlands)).

The results are shown in Table 1.

Table 1

	Density (g / cm 3)
Example 1	1.40
Example 2	1.39
Comparative Example 1	1.26

Referring to Table 1, it can be seen that the film formed using the compositions according to Examples 1 and 2 has a higher density than the film formed using the compositions according to Comparative Example 1. From this, it can be seen that when the compositions according to Examples 1 and 2 are used, a resist underlayer film having a more dense structure can be formed, thereby effectively preventing the penetration of contaminants that can elute from the substrate.

Evaluation-2: Degree of Elution in Solvents and Developers

Propylene glycol monomethyl ether (PGME) sole solvent and propylene glycol monomethyl ether acetate (PGMEA) / cyclohexanone (a solvent mainly used for resist using the resist underlayer film formed from the composition according to Examples 1 and 2 and Comparative Example 1) It was immersed in a 2.38wt% aqueous solution of tetramethyl ammonium hydroxidr (TMAH), which is mainly used as a developer when forming a cyclohexanone or anone (5/5 v / v) mixed solvent and a resist pattern.

The thickness of the initial resist underlayer film and the thickness of the resist underlayer film after immersion were compared to confirm the degree of dissolution in the solvent and the developer.

The results are shown in Table 2.

TABLE 2

	Solvent or developer	Initial thickness	Thickness after immersion	Thickness change	Thickness change rate (%)
Example 1	PGME	107.35	107.46	0.11	0.10
	PGMEA / Anone	104.95	105.16	0.21	0.20
	TMAH	106.96	106.90	-0.06	-0.06
Example 2	PGME	104.06	103.66	-0.40	-0.38
	PGMEA / Anone	104.25	104.22	-0.03	-0.03
	TMAH	105.08	105.16	0.08	0.08
Comparative Example 1	PGME	105.81	103.34	-2.47	-2.33
	PGMEA / Anone	103.27	101.00	-2.27	-2.20
	TMAH	108.83	105.49	-3.34	-3.07

Referring to Table 2, the compositions according to Examples 1 and 2 were little eluted in the solvent or developer used in the resist, whereas the composition according to Comparative Example 1 was eluted in the solvent or developer and the film thickness was significantly reduced. You can see that.

Evaluation-3: Exposure Characteristics

After applying a resist solution on the resist underlayer film formed from the composition according to Examples 1 and 2 and Comparative Example 1 by spin-on coating method, the resist layer was formed by heat treatment at 110 ° C for 1 minute on a hot plate.

The resist layer was exposed using an e-beam exposure machine (Elionix, Acceleration voltage: 100keV) under a line width of 30 nm and a space width of 30 nm. Subsequently, heat treatment was performed at 95 ° C. for 60 seconds, followed by development for 60 seconds with a 2.38 wt% aqueous tetramethylammonium hydroxide (TMAH) and rinsing with pure water for 15 seconds to form a resist pattern.

The resolution, line-width roughness (LWR) and developing residue of the resist pattern were evaluated.

Line-width roughness (LWR) was observed with a scanning electron microscope (SEM) S-9260 (manufactured by Hitachi) for a pattern formed with a width of 30 nm, and the edge was measured for the length edge of the pattern in the range of 2 µm. The distance from the baseline to be measured was measured. The smaller the line-width roughness LWR, the better.

The development residue is based on the dissolution rate (DR) dissolved in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) .The higher the rate, the less the development residue after pattern formation and the degree of decrease. Observation was carried out with a scanning microscope (SEM) to indicate good case ○, insufficient case △, and defective case X.

The results are shown in Table 3.

TABLE 3

	LWR (nm)	Phenomenon residue
Example 1	2.0	○
Example 2	2.2	○
Comparative Example 1	3.8	△

Referring to Table 3, it can be seen that the pattern formed using the compositions according to Examples 1 and 2 is improved in both LWR, resolution and development residue compared to the pattern formed using the composition according to Comparative Example 1.

From this, it can be seen that when the compositions according to Examples 1 and 2 are used as resist underlayer films, all of the film density, solvent elution property and exposure characteristics are improved.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims (11)

1. Cyanuric acid derivatives represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   R ¹ to R ³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

   L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted or unsubstituted C7 to C20 arylalkylene group, substituted or unsubstituted C1 to C20 heteroalkylene group, substituted or unsubstituted C2 to C30 heterocycloalkylene group, substituted or unsubstituted C2 to C30 heteroarylene group, substituted or unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof.
2. In claim 1,

   At least one of the R ¹ to R ³ is a cyanuric acid derivative which is a heterocycloalkyl group or a heteroaryl group containing at least one of nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P).
3. In claim 2,

   Wherein at least one of R ¹ to R ³ is a cyanuric acid derivative selected from formula a, formula b or a combination thereof:

   [Formula a]

   

   [Formula b]

   

   In Chemical Formula a or Chemical Formula b,

   R ⁴ to R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

   * Indicates a linking moiety to sulfur (S) of the formula (1).
4. In claim 1,

   The cyanuric acid derivative may be a cyanuric acid derivative represented by at least one of Chemical Formula 1a and Chemical Formula 1b:

   [Formula 1a]

   

   [Formula 1b]

   
5. Cyanuric acid derivatives including sulfur,

   Photosensitive polymer, and

   menstruum

   A composition for resist underlayer film comprising a.
6. In claim 5,

   The cyanuric acid derivative is a composition for a resist underlayer film represented by the following general formula (1):

   [Formula 1]

   

   R ¹ to R ³ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

   L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 cycloalkenylene group, substituted or unsubstituted C7 to C20 arylalkylene group, substituted or unsubstituted C1 to C20 heteroalkylene group, substituted or unsubstituted C2 to C30 heterocycloalkylene group, substituted or unsubstituted Substituted C2 to C30 heteroarylene group, substituted or unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C30 alkynylene group, or a combination thereof,

   * Indicates a linking moiety to sulfur (S) of the formula (1).
7. In claim 6,

   At least one of R ¹ to R ³ is a heterocycloalkyl group or a heteroaryl group containing at least one of nitrogen (N), sulfur (S), oxygen (O) and phosphorus (P) for a resist underlayer film composition.
8. In claim 7,

   At least one of R ¹ to R ³ is a composition for a resist underlayer film selected from the following formula a, formula b or a combination thereof:

   [Formula a]

   

   [Formula b]

   

   In Chemical Formula a or Chemical Formula b,

   R ⁴ to R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C7 to C20 arylalkyl group, substituted or unsubstituted C1 to C20 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heteroaryl group , Substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, substituted or unsubstituted C1 to C20 aldehyde group, substituted or unsubstituted amino group, halogen group, halogen-containing group or a combination thereof ego,

   * Indicates a linking moiety to sulfur (S) of the formula (1).
9. In claim 5,

   The cyanuric acid derivative and the photosensitive polymer are 0.1 to 5 parts by weight and 0.1 to 30 parts by weight, respectively, based on 100 parts by weight of the solvent.
10. Providing a layer of material over the substrate,

    Applying a composition for resist underlayer film according to any one of claims 5 to 9 on the material layer;

    Heat-treating the composition for resist underlayer film to form a resist underlayer film,

    Forming a resist layer on the resist underlayer film,

    Exposing and developing the resist layer to form a resist pattern,

    Selectively removing the resist underlayer film using the resist pattern and exposing a portion of the material layer; and

    Etching the exposed portion of the material layer

    Pattern forming method comprising a.
11. In claim 10,

    The forming of the resist underlayer film is performed by a spin-on coating method.