KR102396715B1 - Process of preparing hardmask film including metal and forming resist pattern - Google Patents

Abstract

The present invention relates to a method for forming a metal-containing hard mask film by coating a substrate with a composition for forming a hard mask containing a metal-containing compound and then irradiating the composition or the primarily cured hard mask film with a laser, and a method for forming a resist pattern using the same. In the hard mask film prepared according to the present invention, the content of components having strong binding energy increases, and the content of components having weak binding energy decreases. In an etching process for forming a pattern, the etch resistance of the hard mask film is improved, so the present invention can be used to manufacture semiconductor devices and display devices having an intended fine pattern.

Description

Method for manufacturing a metal-containing hard mask film and forming a resist pattern TECHNICAL FIELD

The present invention relates to a method of manufacturing a hardmask film, and more particularly, to a method of manufacturing a metal-containing hardmask film applied to a photoresist process and a method of forming a resist pattern using the same.

Semiconductor devices, including memory devices, required in the process of manufacturing semiconductors are gradually becoming smaller and more highly integrated. As semiconductor devices are highly integrated, it is necessary to form a finer pattern than a conventional semiconductor device pattern when manufacturing a semiconductor device. A resist pattern using a photolithography process using a light source, which is currently used as a general-purpose technology for manufacturing semiconductor devices, is adopted.

The light source used in the photolithography process used to form the resist pattern is g-line (436 nm) and i-line (365 nm) using a mercury lamp. Laser) (248 nm) and ArF excimer laser (193 nm), etc., are mainly used for the photolithography process. Recently, a photolithography process using EUV (Extreme Ultraviolet) with a shorter wavelength of 13.5 nm as a light source is in the commercialization stage. .

In the case of using an ArF excimer laser light source, which is generally used in a photolithography process for forming a pattern of a semiconductor device, there is a limitation in intrinsic resolution derived from the wavelength of the light source. As a method to overcome this and form a finer pattern, a double patterning technology that implements an ultra-fine pattern by repeating the photolithography process twice, and a double patterning technology that performs the exposure process twice to obtain a pattern with a desired resolution After performing the double expose patterning technology or exposure process once, a spacer is formed on the sacrificial layer pattern by Chemical Vapor Deposition (CVD) method and the sacrificial film is removed. A spacer patterning technology for obtaining a pattern with a desired resolution has been proposed and is currently being applied to a mass production process of a semiconductor device.

However, it is impossible to directly etch a semiconductor substrate such as a silicon wafer using a fine resist pattern. Accordingly, an underlayer process of introducing a resist underlayer or hardmask film between the resist film and the semiconductor substrate, patterning the underlayer or hardmask film, and then etching the substrate is generally applied.

The resist underlayer film is made of silicon nitride (SiN _x ), silicon oxynitride (SiO _x N _y ), polysilicon, titanium nitride, amorphous carbon, etc., and is typically chemical vapor deposition (chemical vapor deposition). : It is formed by CVD) method.

An amorphous carbon material with excellent etch selectivity and etch resistance was used as an underlayer material for the etching process for forming fine patterns. However, since the resist underlayer is formed through the deposition process, the lower step is reflected in the underlayer as it is. In addition, when the resist underlayer is formed, a void is generated due to pattern refinement, which makes it difficult to proceed with the planarization process. In addition, since expensive equipment such as a vacuum deposition apparatus is required to form the resist underlayer, the initial investment cost is high and the productivity of the process is low.

As described above, in order to satisfy the demand for pattern miniaturization according to the increase in the degree of integration of semiconductor devices, and to improve device characteristics and data storage capability, the steps of semiconductor devices are being formed higher. As such, by forming a fine pattern through an effective etching process with a high step difference, uniform device characteristics and a high manufacturing yield can be secured.

In particular, in the case of 3D NAND, the importance of an effective etching process is further emphasized considering the continuously increasing number of stages. As a hard mask film in the etching process for fine patterning, an amorphous carbon film was mainly applied. However, the productivity is greatly reduced due to the long-term process due to the high-thickness deposition, and problems such as wafer shrinkage are generated due to the influence of the high-temperature deposition process. In order to solve the problems of the existing amorphous carbon film, a hard mask applied with a carbon-based material for a spin coating process with good productivity has been developed, but it is difficult to implement a high thickness due to weak etching resistance.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a metal-containing hardmask film capable of enhancing etch resistance and a method for forming a resist pattern using the same.

Another object of the present invention is to provide a method of manufacturing a metal-containing hardmask film capable of minimizing substrate shrinkage and a method of forming a resist pattern using the same.

Another object of the present invention is to provide a method for manufacturing a metal-containing hardmask film with improved physical properties without using expensive deposition equipment and heat treatment equipment, and a method for forming a resist pattern using the same.

According to one aspect, the present invention comprises the steps of coating a composition for forming a hard mask comprising a metal-containing compound having a structure of Formula 1 on a substrate; It provides a method of manufacturing a metal-containing hard mask film comprising irradiating a laser to the composition for forming a hard mask so that the metal-containing compound is cured to form a hard mask film.

[Formula 1]

In Formula 1, M ¹ is a metal of Groups 3 to 16 of the Periodic Table; M ² is selected from the group consisting of metals of Groups 3 to 16 of the periodic table, C, Si, B, P and S; R is hydrogen or a C ₁ -C ₃₀ hydrocarbyl group; L ¹ and L ² are each independently a ligand selected from Formula 2 below; A is a linking group having a structure of Formula 4, Formula 5, or Formula 6; m is an integer from 1 to 100; n is an integer from 0 to 100; p and q are each independently an integer from 0 to 6.

[Formula 2]

In Formula 2, R ¹ to R ⁴ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ¹ ; M ³ is selected from the group consisting of Li, C, Si, B, P, S and a metal from Groups 3 to 16 of the periodic table; L ₃ is a ligand selected from the following formula (3); r is an integer from 0 to 6; An asterisk indicates a site connected to M ¹ or M ² in Formula 1; Q ¹ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 3]

In Formula 3, R ¹¹ to R ¹³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ² ; An asterisk indicates a site connected to M ³ of Formula 2; Q ² is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 4]

[Formula 5]

[Formula 6]

In Formula 4, L ⁴ and L ⁵ are each independently a C ₁ -C ₂₀ alkylene group, a C ₂ -C ₂₀ alkylene group having a carbon-carbon double bond, a C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond, C ₃ -C ₂₀ cycloalkylene group, C ₆ -C ₃₀ arylene group, C ₃ -C ₃₀ hetero arylene group, the C ₁ -C ₂₀ alkylene group, C ₂ -C ₂₀ alkyl having a carbon-carbon double bond The ene group and the C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond may each independently be unsubstituted or substituted with at least one Q ³ ; D is a direct bond, NR ¹⁴ , O or S, and R ¹⁴ is a hydrogen atom, a hydroxy group, a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group; Q ³ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formula 5, R ²¹ and R ²² are each independently selected from the group consisting of a hydrogen atom, a C ₁ -C ₁₀ alkyl group, and a C ₆ -C ₂₀ aryl group; s is an integer from 1 to 1000.

In Formula 6, M ⁴ is selected from the group consisting of Li, C, Si, B, P, S, and metals of Groups 3 to 16 of the periodic table; L ⁶ is a hydrogen atom, a halogen atom, =O, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group , C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ It is selected from the group consisting of a heteroaryl alkyl group and a ligand having a structure of Formula 7 below, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ - Each C ₂₀ alkoxy group may be independently unsubstituted or substituted with at least one Q ⁴ ; t is an integer from 0 to 6; Q ⁴ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group; In Formulas 4 to 6, an asterisk represents a connection site, respectively.

[Formula 7]

In Formula 7, R ³¹ to R ³³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ⁵ ; An asterisk indicates a site connected to M ⁴ in formula (6); Q ⁵ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

For example, the wavelength of the laser may be 10 to 700 nm, for example, 10 to 400 nm.

Optionally, the laser may be selected from the group consisting of an ion laser, a molecular laser, an excimer laser, and a combination thereof, and in particular may include an excimer laser.

For example, the content of the metal component in the metal-containing compound may be 5 to 70 wt%.

In this case, the content of carbon in the metal-containing compound is 10 to 60% by weight, the content of oxygen is 10 to 60% by weight, and the remaining amount of hydrogen may be included.

In the step of irradiating the laser, the laser may be irradiated with an intensity of 10 to 5000 mW per cm 2 .

The step of irradiating the laser may be performed for 1 minute to 10 minutes, and the step of irradiating the laser may be performed 1 to 10 times.

In the step of irradiating the laser, the laser may be irradiated at a distance of 1 to 250 mm from the composition for forming a hard mask.

The method may further include performing a heat treatment on the composition for forming a hard mask between the coating step and the step of irradiating the laser.

In this case, compared with the metal content in the cured product of the metal-containing compound having the structure of Formula 1 present in the hardmask film after performing the heat treatment, the metal present in the hardmask film after irradiating the laser The metal content in the cured product of the containing compound may be increased by 5 to 70%.

The heat treatment may be performed at 150 to 500° C. for 30 seconds to 10 minutes.

The composition for forming a hard mask may further include an organic solvent.

Optionally, the composition for forming a hard mask may further include a compound for enhancing thickness.

For example, the compound for enhancing the thickness may include an organic compound having a repeating structure of Formula 8 below.

[Formula 8]

In Formula 8, R ⁴¹ and R ⁴² are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ heteroaryl alkyl group and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁶ ; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ hetero aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ hetero It is selected from the group consisting of an aryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁷ . has exist; L ⁷ is a linking group selected from the following formula (9); B is selected from the following formula (10); Q ⁶ and Q ⁷ are each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 9]

[Formula 10]

In Formula 9, Y is each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, a carboxy group, a nitro group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, Amino group, C ₁ -C ₂₀ alkyl amino group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ It is selected from the group consisting of an aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or may be substituted with at least one Q ⁸ ; Q ⁸ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formula 10, each Z is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, and a C ₆ -C ₃₀ selected from the group consisting of an aryl group, a C ₆ -C ₃₀ aryloxy group, a C ₃ -C ₃₀ heteroaryloxy group, a C ₇ -C ₃₀ aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, wherein the C ₁ - The C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group may each independently be unsubstituted or substituted with at least one Q ⁹ ; Q ⁹ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formulas 9 and 10, an asterisk indicates a connection site.

In an exemplary aspect, in the composition for forming a hard mask, the compound for enhancing the thickness may be added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the metal-containing compound having the structure of Formula 1 above.

The step of coating the composition for forming the hard mask is selected from the group consisting of spin coating, slot die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, bar coating, slit coating, and combinations thereof. can be

In another aspect, the method comprising: forming a resist film on the hard mask film produced by the above method; exposing the resist film; and developing the exposed resist film to form a patterned resist film.

When forming a resist pattern, after forming the patterned resist film, etching the hard mask film based on the patterned resist film to form a patterned hard mask film, and the patterned hard mask film The method may further include etching the substrate based on the substrate to form a patterned substrate.

In the step of forming the patterned hardmask layer, the etching process may be performed under a gas atmosphere composed of nitrogen, hydrogen, oxygen, helium, neo, argon, and combinations thereof.

In the step of forming the patterned hardmask layer, an etching process may be performed by a plasma etching process.

For example, in the step of forming the patterned hardmask layer, the etching treatment is performed using a gas composed of CHF ₃ , CF _{4 ,} BCl ₃ , Cl ₂ , SF ₆ , nitrogen, oxygen, argon, and combinations thereof. can be

Optionally, before forming the resist film, the method may further include forming an intermediate layer on the hardmask film.

In this case, after forming the patterned resist film, etching the interlayer film based on the patterned resist film to form a patterned interlayer film, and etching the hardmask film based on the patterned interlayer film The method may further include forming a patterned hardmask layer and etching the substrate based on the patterned hardmask layer to form a patterned substrate.

For example, the interlayer film may include a lower anti-reflection film.

Optionally, the interlayer film may be made of a material selected from the group consisting of titanium nitride, titanium oxynitride, silicon oxide, silicon oxynitride, silicon nitride, an amorphous carbon-based material, and combinations thereof.

In another aspect, the present invention provides a semiconductor device manufactured through the above-described pattern forming method.

The present invention proposes a method of manufacturing a hardmask film in which a composition for forming a metal-containing hardmask is coated on a substrate and then curing a metal compound by irradiating a laser, and a method of forming a resist pattern using the same.

By laser irradiation, organic components having a low bonding energy are removed from the composition for forming a hard mask, and the content of components having a strong bonding is increased. Accordingly, thermal stability and etch resistance are improved, and a hard mask film having excellent etch selectivity can be manufactured.

Accordingly, it is possible to form a low resist film disposed on the hardmask film having an excellent etch selectivity, thereby improving pattern resolution and pattern roughness to implement a uniform pattern. Even in the high-temperature process of forming a resist pattern, the hardmask film of the present invention is not damaged, and a desired pattern can be realized by minimizing irregularities in the profile of the pattern formed after etching.

In addition, since the composition for forming a hard mask is cured using light rather than heat, shrinkage of the lower substrate due to thermal energy can be minimized. In addition, since the metal-containing hard mask film is formed using a coating process without using expensive deposition equipment and heat treatment equipment, the production rate can be reduced in the process of forming the hard mask film and the resist pattern using the same, and the pattern defect It is possible to maximize the production yield of the device by minimizing the

Accordingly, the present invention can be utilized to manufacture a semiconductor device and/or a display device having a fine pattern structure.

1 to 4 are diagrams schematically illustrating a cross section of a substrate and a hard mask film in a process of forming a hard mask film including a metal-containing compound according to the present invention, and a composition of a metal compound in the hard mask film, respectively. 1 shows a substrate, FIG. 2 shows a state in which the composition for forming a hard mask is coated on the substrate, FIG. 3 shows a state in which heat treatment is optionally performed on the composition for forming a hard mask, and FIG. 4 is a hard mask film. Indicates the state in which the laser is irradiated.
5 to 7 are views schematically showing cross-sections of a substrate, a hardmask film, an interlayer film, and a resist film in the process of forming a resist pattern using a hardmask film containing a metal compound according to the present invention. FIG. 5 shows a state in which an intermediate layer film and a resist film are sequentially disposed on the hardmask film of the present invention used as an underlayer film, FIG. 6 shows a state in which a patterned resist film is formed by an exposure process and a developing process, and FIG. 7 denotes a patterned interlayer film, a patterned hardmask film and a patterned substrate using the patterned resist film as a mask.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings, if necessary.

[Formation of metal-containing hard mask film]

According to the present invention, physical properties such as etching resistance of the hardmask film can be improved by irradiating a laser to the composition for forming a metal-containing hardmask or selectively heat-treated preliminary hardmask film. A process for manufacturing the metal-containing hardmask film will be described first. 1 to 4 are diagrams schematically illustrating a cross section of a substrate and a hard mask film in a process of forming a hard mask film including a metal-containing compound according to the present invention, and a composition of a metal compound in the hard mask film, respectively.

As shown in FIG. 1 , a substrate 10 is prepared. In an exemplary aspect, the substrate 10 may include a packaging substrate such as a multi-chip module; flat panel display substrates; integrated circuit board; a substrate for a light emitting diode (LED) including an organic light emitting diode (OLED); semiconductor wafer; and a polycrystalline silicon substrate. In one example, the substrate 10 may include silicon, polysilicon, silicon, silicon oxide (SiO _x ), silicon nitride (SiN _x ) and/or silicon oxynitride (SiO _x N _y ), silicon germanium, gallium arsenide, It may be made of a material selected from the group consisting of aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, gold, and combinations thereof.

For example, the substrate 10 may be in the form of a wafer, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Optionally, a material layer to be finally patterned may be included on the substrate 10 . The material layer may be a semiconductor layer made of silicon, or an insulating layer made of silicon oxide (SiO _x ), silicon nitride (SiN _x ) and/or silicon oxynitride (SiO _x N _y ). The material layer may be formed using, for example, chemical vapor deposition (CVD).

Next, as shown in FIG. 2 , a composition 20A for forming a metal-containing hard mask is coated on the prepared substrate 10 . As will be described later, the hardmask-forming composition 20A may be cured to form a metal-containing hardmask film.

The metal-containing hard mask can secure all the advantages of the hard mask used in the past as a coating method. The metal-containing hardmask film has excellent etch selectivity compared to an amorphous carbon layer (ACL). Therefore, when the metal-containing hard mask is applied, the thickness of the resist film disposed thereon can be reduced, and thus the resolution of the fine pattern can be improved. In addition, by applying a metal-containing hardmask film, the process margin is improved, and the roughness of the pattern formed during downward etching is improved, thereby forming a uniform pattern, thereby improving device characteristics. In addition, it can contribute to the improvement of the yield of semiconductor devices by securing excellent gap-fill and planarization characteristics in various lower steps according to the application of the coating method of the material.

Above all, the metal-containing hard mask film can obtain the effect of reducing equipment investment due to superior productivity compared to the deposition process of the amorphous carbon hard mask film according to the application of the coating method. In addition, since the metal-containing hardmask film does not have a warpage problem occurring in the thick deposition substrate 10 , it can contribute to improving the yield by securing stable device characteristics. However, when forming a cured hardmask film from the composition 20A for forming a hardmask, a high-temperature heat treatment process is essential. Due to the heat generated in the heat treatment process, the network structure of the cured metal-containing compound is collapsed, and cracks are generated in the finally manufactured metal-containing hard mask film. In addition, since the content of organic components is high in the metal-containing hard mask film manufactured by the heat treatment process, etching resistance is lowered in the process of forming the resist pattern, making it difficult to sufficiently implement a desired pattern. In the present invention, in order to improve the problems of the metal-containing hardmask film, it is possible to implement a metal-containing hardmask film having improved physical properties such as etching resistance by irradiating laser light. The laser irradiation process and the like will be described later.

The composition 20A for forming a hard mask coated on the substrate 10 may include a metal-containing compound and an organic solvent, and may optionally include a compound for enhancing thickness, a polyol, and an additive. The metal containing compound may be a cluster compound which may be a metal cluster compound and/or a metal-oxo cluster compound.

For example, the metal-containing compound added to the composition 20A for forming a hard mask may have the structure of Formula 1 below.

[Formula 1]

In Formula 1, M ¹ is a metal of Groups 3 to 16 of the Periodic Table; M ² is selected from the group consisting of metals of Groups 3 to 16 of the periodic table, C, Si, B, P and S; R is hydrogen or a C ₁ -C ₃₀ hydrocarbyl group; L ¹ and L ² are each independently a ligand selected from Formula 2 below; A is a linking group having a structure of Formula 4, Formula 5, or Formula 6; m is an integer from 1 to 100; n is an integer from 0 to 100; p and q are each independently an integer from 0 to 6.

[Formula 2]

In Formula 2, R ¹ to R ⁴ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ¹ ; M ³ is selected from the group consisting of Li, C, Si, B, P, S and a metal from Groups 3 to 16 of the periodic table; L ₃ is a ligand selected from the following formula (3); r is an integer from 0 to 6; An asterisk indicates a site connected to M ¹ or M ² in Formula 1; Q ¹ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 3]

In Formula 3, R ¹¹ to R ¹³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ² ; An asterisk indicates a site connected to M ³ of Formula 2; Q ² is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 4]

[Formula 5]

[Formula 6]

In Formula 4, L ⁴ and L ⁵ are each independently a C ₁ -C ₂₀ alkylene group, a C ₂ -C ₂₀ alkylene group having a carbon-carbon double bond, a C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond, C ₆ -C ₃₀ arylene group, C ₃ -C ₂₀ cycloalkylene group, C ₃ -C ₃₀ hetero arylene group, the C ₁ -C ₂₀ alkylene group, C ₂ -C ₂₀ alkyl having a carbon-carbon double bond The ene group and the C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond may each independently be unsubstituted or substituted with at least one Q ³ ; D is a direct bond, NR ¹⁴ , O or S, and R ¹⁴ is a hydrogen atom, a hydroxy group, a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group; Q ³ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formula 5, R ²¹ and R ²² are each independently selected from the group consisting of a hydrogen atom, a C ₁ -C ₁₀ alkyl group, and a C ₆ -C ₂₀ aryl group; s is an integer from 1 to 1000.

In Formula 6, M ⁴ is selected from the group consisting of Li, C, Si, B, P, S, and metals of Groups 3 to 16 of the periodic table; L ⁶ is a hydrogen atom, a halogen atom, =O, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group , C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ It is selected from the group consisting of a heteroaryl alkyl group and a ligand having a structure of Formula 7 below, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ - Each C ₂₀ alkoxy group may be independently unsubstituted or substituted with at least one Q ⁴ ; t is an integer from 0 to 6; Q ⁴ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group; In Formulas 4 to 6, an asterisk represents a connection site, respectively.

[Formula 7]

In Formula 7, R ³¹ to R ³³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ⁵ ; An asterisk indicates a site connected to M ⁴ in formula (6); Q ⁵ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In an exemplary aspect, the metal-containing compound is a metal cluster and/or metal-oxo (indicated by OR in FIG. 2) having a three-dimensional structure in which three or more atoms of the same element or a plurality of kinds of elements are gathered and combined into one mass. It may be a cluster compound. For example, the cluster compound has a three-dimensional structure in which three or more elements form a ring-shaped or non-cyclic group, and a plurality of the ring-shaped or non-cyclic groups form a cluster. It may be a compound having

The metal-containing compound may further include at least one ligand represented by Formula (2). Optionally, the metal-containing compound may have a polyhedral structure. For example, the polyhedron structure may be, but is not limited to, an octahedron, a decahedron, a dodecahedron, an icosahedron, or a trisoctahedron.

In an exemplary aspect, when M ¹ , M ² , M ³ and M ⁴ in Formula 1, Formula 2, and Formula 6 are metal components, the metal component (indicated as M in FIG. 2 ) is an alkali metal, an alkaline earth metal, It may be selected from the group consisting of transition metals, post-transition metals, metalloids, and combinations thereof. For example, the metal component of the metal-containing compound is Li, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Y, Zr, Nb, Mo , Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po and combinations thereof It can be selected from the group consisting of.

In an optional aspect, the metal component in the metal-containing compound may be at least one metal belonging to Groups 3 to 16 of the Periodic Table. In another optional aspect, the metal component in the metal-containing compound may be at least one metal belonging to Periods 3 to 6 of the Periodic Table. In another optional aspect, the metal component in the metal-containing compound may be at least one metal belonging to Periods 3 to 6 of the Periodic Table, and Groups 4, 6, and 13 to 16 of the Periodic Table.

In another exemplary aspect, the metal component in the metal-containing compound may be selected from the group consisting of Zr, Ti, Al, Ga, Hf, In, Sn, Sb, W, Tl, Pb, Bi, Po, and combinations thereof. there is. For example, the metal component in the metal-containing compound may be selected from the group consisting of Zr, Ti, Al, Hf, In, Sn, and combinations thereof, but is not limited thereto.

As shown in Formula 1, in the metal-containing compound which may be a cluster compound, the metal component may be one or a plurality of two or more. The plurality of metals may be the same as or different from each other. In addition, metal-containing compounds may have one or more organic substituents bonded to the metal (OR or ligands such as L ¹ and L ² ), oxo bonds between metal-oxygen and/or optionally within the metal and organic substituents. It may include a metal-carbon bond to which carbon is bonded.

According to another exemplary aspect, when R in Formula 1 is a C ₁ -C ₃₀ hydrocarbyl group, R is a C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₃ -C ₃₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ hetero aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group, C ₄ -C ₃₀ heteroaryl alkyl group , it may be selected from the group consisting of a carbonyl group, a carboxy group, an ester group, and an amide group.

For example, in Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ to R ³³ and L ⁶ C ₁ -C ₂₀ that may each constitute Alkyl groups include linear or branched alkyl groups and include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl. , hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, but is not limited thereto.

In Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ to R ³³ and a C ₂ -C ₂₀ alkenyl group that may each constitute L ⁶ are at least It is a linear or branched hydrocarbon group having one carbon-carbon double bond. In Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ₁₄ , R ²¹ , R ₂₂ , R ³¹ to R ³³ and L ⁶ A C ₂ -C ₂₀ alkynyl group that may each constitute at least It is a linear or branched hydrocarbon group having one carbon-carbon triple bond.

In Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ to R ³³ and L ⁶ A C ₁ -C ₂₀ alkoxy group that may each constitute an ether bond It is a hydrocarbon group to which the aforementioned linear or branched alkyl group is connected through. Alkoxy groups may include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy and tert-butoxy.

In Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ to R ³³ and L ⁶ C ₃ -C ₂₀ cycloalkyl groups that may each constitute a ratio -Aromatic carbon-based ring compound, including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbonyl.

In Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ¹⁴ , R ²¹ , R ²² , R ³¹ to R ³³ and C ₆ -C ₃₀ aryl groups that may constitute L ⁶ are each independently Rhophenyl, biphenyl, terphenyl, naphthyl, anthracenyl, pentalenyl, indenyl, indenoindenyl, heptalenyl, biphenylenyl, indacenyl, phenalenyl, phenanthrenyl, benzophenanthrenyl, dibenzophenane Trenyl, azulenyl, pyrenyl, fluoranthenyl, triphenylenyl, chrysenyl, tetraphenyl, tetracenyl, pleidaenyl, pycenyl, pentaphenyl, pentacenyl, fluorenyl, indenofluorenyl or an uncondensed or fused aryl group such as spiro fluorenyl.

In addition, in Formulas 1 to 7, R, R ¹ to R ⁴ , R ¹¹ to R ₁₄ , R ²¹ , R ₂₂ , R ³¹ to R ³³ and L ⁶ C ₃ -C ₃₀ heteroaryl that may each constitute each group is independently pyrrolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, tetrazinyl, imidazolyl, pyrazolyl, indolyl, isoindolyl, indazolyl, indolizinyl, pyrrolyl Zinyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, benzofurocarbazolyl, benzothienocarbazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoc Salinyl, cinolinyl, quinazolinyl, quinozolinyl, quinolinyl, purinyl, benzoquinolinyl, benzoisoquinolinyl, benzoquinazolinyl, benzoquinoxalinyl, acridinyl, phenanthrolinyl , ferimidinyl, phenanthridinyl, pteridinyl, naphtharidinyl, furanyl, pyranyl, oxazinyl, oxazolyl, oxadiazolyl, triazolyl, deoxynyl, benzofuranyl, dibenzofuranyl, Thiophyranyl, xanthenyl, chromenyl, isochromenyl, thioazinyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, difuropyrazinyl, benzofurodibenzofuranyl, benzothienobenzothiophenyl, uncondensed or fused heteroaryl groups such as benzothienodibenzothiophenyl, benzothienobenzofuranyl, benzothienodibenzofuranyl or N-substituted spiro fluorenyl.

The C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or at least one monovalent or divalent carbonyl group , for example, a ketone group, an aldehyde group, an ester group, and a carboxy group may be substituted in the middle of the chain or at the end of the chain.

Meanwhile, in Formula 4, L ₄ and L ⁶ may be a C ₁ -C ₂₀ alkylene group, a C ₂ -C ₂₀ alkylene group having a carbon-carbon double bond, or a C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond. , C ₃ -C ₂₀ cycloalkylene group, C ₆ -C ₃₀ arylene group, C ₃ -C ₃₀ hetero arylene group respectively corresponding to the aforementioned alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group and heteroaryl group, respectively It may be a divalent organic group. A C ₁ -C ₂₀ alkylene group, a C ₂ -C ₂₀ alkylene group having a carbon-carbon double bond, and a C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond are each independently unsubstituted or at least one It may be substituted with a carbonyl group.

In another optional aspect, in Formula 1, m may be an integer from 1 to 10, such as 1 to 5 or 1 to 2, and n may be an integer from 0 to 10, such as 0 to 5 or 0 to 2, However, the present invention is not limited thereto. In another optional aspect, in Formulas 1, 2, and 6, p, q, r and t may each independently be an integer of 0 to 4, for example, an integer of 0 to 2, but is not limited thereto. In another optional aspect, in Formula 5, s may be an integer of 1 to 100, for example, an integer of 1 to 50, or an integer of 1 to 10, but is not limited thereto.

In one exemplary aspect, the content of the metal component in the metal-containing compound that may have the structure of Formula 1 may be 5 to 70% by weight, for example, 10 to 40% by weight or 10 to 30% by weight. When the content of the metal component in the metal-containing compound is less than 5% by weight, the etching resistance of the hard mask layer is deteriorated, and it may be difficult to achieve sufficiently improved etching resistance even by a laser irradiation process to be described later. On the other hand, when the content of the metal component in the metal-containing compound exceeds 70% by weight, solubility in an organic solvent may decrease, and cracks may occur in the hardmask film manufactured by the heat treatment process or the laser irradiation process. .

The content of the carbon component in the metal-containing compound that may have the structure of Formula 1 may be 10 to 60 wt%, for example, 20 to 50 wt%. When the content of the carbon component in the metal-containing compound is less than 10% by weight, solubility in an organic solvent may decrease. When the content of the carbon component in the metal-containing compound exceeds 60% by weight, the content of the carbon component relative to the content of the metal component is excessively increased, so that the etching resistance may be reduced.

The content of the oxygen component in the metal-containing compound which may have the structure of Formula 1 may be 10 to 60 wt%, for example, 30 to 50 wt%. When the content of the oxygen component in the metal-containing compound is less than 10% by weight, the metal stabilization effect is reduced, and storage stability of the composition 20A for forming a hard mask may be reduced, as well as the solubility of the metal-containing compound may be reduced. When the content of the oxygen component in the metal-containing compound exceeds 60% by weight, etching resistance may deteriorate.

The composition 20A for forming a hard mask may include an organic solvent capable of dispersing and dissolving the metal-containing compound and the compound for thickness enhancement to be described later. The organic solvent may include an alcohol-based organic solvent, an ester-based organic solvent, a ketone-based organic solvent, a diketone-based organic solvent, a carboxylic acid-based organic solvent, an amide-based organic solvent, an aromatic-based organic solvent, and combinations thereof. Specifically, the organic solvent is a lower alcohol (C ₁ -C ₆ ), such as isopropanol, n-butanol, t-butanol, 1-pentanol and 4-methyl-2-pentanol; glycols such as ethylene glycol and propylene glycol; diketones such as diacetyl, acetylacetone, and hexane-2,5-dione; glycol ether derivatives such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate; carboxylates such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylates of dibasic acids such as diethyloxylate and diethylmalonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; hydroxy carboxylates such as methyllactate, ethyllactate, ethylglycolate, and ethyl-3-hydroxy propionate; ketone esters such as methyl pyruvate or ethyl pyruvate; Alkoxy alcohols such as 1-methoxy-2-propanol, 2-methoxyethanol, ethoxyethanol, alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; ketone derivatives such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives such as diacetone alcohol methyl ether; ketone alcohol derivatives such as acetol or diacetone alcohol; lactones such as butyrolactone and gamma-bellarolactone; amide derivatives such as dimethylacetamide or dimethylformamide, aromatic solvents such as anisole, and combinations thereof.

In an optional aspect, the composition 20A for forming a hard mask may further include a compound for enhancing thickness. By including the compound for enhancing the thickness, it is possible to prevent or minimize the reduction in the thickness of the composition 20A for forming the hard mask during the curing process of forming the hard mask film. In an exemplary aspect, the compound for enhancing the thickness may include an organic compound having a repeating structure of Formula 8 below, but is not limited thereto.

[Formula 8]

In Formula 8, R ⁴¹ and R ⁴² are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ heteroaryl alkyl group and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁶ ; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ hetero aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ hetero It is selected from the group consisting of an aryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁷ . has exist; L ⁷ is a linking group selected from the following formula (9); B is selected from the following formula (10); Q ⁶ and Q ⁷ are each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

[Formula 9]

[Formula 10]

In Formula 9, Y is each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, a carboxy group, a nitro group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, Amino group, C ₁ -C ₂₀ alkyl amino group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ It is selected from the group consisting of an aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or may be substituted with at least one Q ⁸ ; Q ⁸ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formula 10, each Z is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, and a C ₆ -C ₃₀ selected from the group consisting of an aryl group, a C ₆ -C ₃₀ aryloxy group, a C ₃ -C ₃₀ heteroaryloxy group, a C ₇ -C ₃₀ aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, wherein the C ₁ - The C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group may each independently be unsubstituted or substituted with at least one Q ⁹ ; Q ⁹ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.

In Formulas 9 and 10, an asterisk indicates a connection site.

In an exemplary aspect, the compound for enhancing the thickness in the composition 20A for forming a hard mask may be added in an amount of 0.1 to 20 parts by weight, for example, 1 to 10 parts by weight based on 100 parts by weight of the above-described metal-containing compound. . When the content of the compound for enhancing the thickness is less than 0.1 parts by weight based on 100 parts by weight of the metal-containing compound, the effect of inhibiting the thickness reduction of the hard mask film may be insignificant. When the content of the compound for enhancing the thickness exceeds 20 parts by weight based on 100 parts by weight of the metal-containing compound, the content of the organic component in the hardmask layer is excessively increased, and etching resistance may decrease.

When the composition 20A for forming a hard mask is used as a resist underlayer, the composition 20A for forming a hard mask includes additives such as polyols, surfactants, adhesion improvers, crosslinking agents, thermal acid generators, stabilizers, leveling agents, and antifoaming agents. may further include.

For example, the polyol may have a boiling point of 250° C. or more, for example 300° C. or more, and a weight average molecular weight of 500 or less, for example 300 or less. The polyol may be selected from the group consisting of glycerol, triethylene glycol, tetraethylene glycol, neopentyl glycol, glycerol propoxylate, pentaerythritol ethoxylate, diethanolamine, triethanolamine, and combinations thereof, but is not limited thereto. does not

The surfactant improves adhesion properties between the composition 20A for forming a hard mask film and the substrate 10 . The type of surfactant that can be used is not particularly limited, and one or two or more types of nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants may be used in combination. For example, the surfactant may include a fluorine-based surfactant such as a fluoroalkyl-based compound, an alkylbenzenesulfonate, an alkylpyridinium salt, polyethylene glycol, a quaternary ammonium salt, a silicone-based surfactant, and combinations thereof. More specifically, the surfactant or leveling agent may include, but is not limited to, polyethylene glycol dodecyl ether, polyoxyethylene oleyl ether, polyethylene glycol octadecyl ether, polyethylene glycol tert-octylphenyl ether, and combinations thereof. .

Cross-linking agents induce cross-linking reactions between metal-containing compounds. The crosslinking agent is not particularly limited, and examples thereof include melamine-based, substituted urea-based and/or polymer-based agents thereof. For example, as a crosslinking agent having at least two crosslinking substituents, for example, methoxymethylated glycouryl, butoxymethylated glycouryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxy A compound such as methylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or butoxymethylated thiourea may be used.

Optionally, a crosslinking agent having high heat resistance may be used as the crosslinking agent. As a crosslinking agent with high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (eg, a benzene ring, a naphthalene ring) in the molecule can be used.

The thermal acid generator may help a crosslinking reaction between the metal-containing compound when the coated composition for forming a hard mask is cured. Illustratively, the thermal acid generator may be activated at a temperature of 90 °C or higher, for example 120 °C or higher, or 150 °C or higher. Thermal acid generators include metal-free sulfonium salts and iodonium salts, such as triarylsulfonium, dialkylarylsulfonium, and diarylalkylsulfonium salts of strongly non-nucleophilic acids; alkylaryliodonium, diaryliodonium salts of strongly non-nucleophilic acids; and ammonium, alkylammonium, dialkylammonium, trialkylammonium, tetraalkylammonium salts of strongly non-nucleophilic acids. In an optional aspect, the thermal acid generator is diaryliodonium perfluoroalkylsulfonate, diaryliodonium tris(fluoroalkylsulfonyl)methide, diaryliodonium bis(fluoroalkylsulfonyl) methide, diaryliodonium bis(fluoroalkylsulfonyl)imide, diaryliodonium or quaternary ammonium perfluoroalkylsulfonate.

The content of the above-mentioned additives is not particularly limited as long as the physical properties of the hard mask film can be improved, but 0.001 to 40 parts by weight, for example, 0.01 to 30 parts by weight, 0.1 to 20 parts by weight based on 100 parts by weight of the composition for forming a hard mask. It may be included in an amount of 0.1 to 10 parts by weight.

A method of coating the composition 20A for forming a hard mask on the substrate 10 is not particularly limited. As an example, the method of coating the composition 20A for forming a hard mask on the substrate 10 is spin coating such as a central drop spin method, slot die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, A method such as slit coating using a slit nozzle such as bar coating or discharge nozzle type coating may be used, and two or more coating methods may be combined for coating.

For example, the composition 20A for forming a hard mask may be coated on the substrate 10 by spinning the composition 20A for forming a hard mask at a speed of 500 to 4000 rpm for 15 to 90 seconds using spin coating, but is not limited thereto. At this time, the thickness of the coated composition 20 for forming a hard mask may vary depending on the coating method, the concentration of solids in the composition 20A for forming a hard mask, viscosity, etc., but 50 to 2000 nm, for example 50 to 500 nm Alternatively, it may be coated to a thickness of 100 to 300 nm.

After coating the composition 20A for forming a hard mask on the substrate 10, optionally, as shown in FIG. 3, heat treatment is performed on the composition for forming a hard mask, so that the metal-containing compound is primarily cured of a preliminary hard mask. A film 20B is formed. By heat treatment, the metal-containing compound may be partially cured and connected while having a network structure through an oxo bond (-O-).

In the heat treatment process for forming the preliminary hardmask layer 20B, the heat treatment may be performed at 150 to 500° C., for example, at 250 to 450° C. for 30 seconds to 10 minutes, for example, 30 seconds to 5 minutes. For example, the heat treatment process may be performed using a hot-plate or a convection oven to remove the organic solvent in the composition 20A for forming a hard mask to induce curing of the metal-containing compound.

When the heat treatment temperature is less than 150° C. and/or the heat treatment time is less than 30 seconds, the metal-containing compound may not be sufficiently cured. On the other hand, when the heat treatment temperature exceeds 500° C. and/or the heat treatment time exceeds 10 minutes, the molecular structure of the metal-containing compound constituting the hard mask film 20B is collapsed and cracks are formed in the hard mask film 20B. can occur

Even after the heat treatment process, various organic components such as ligands remain in the preliminary hardmask layer 20B. When the content of the organic component in the preliminary hardmask layer 20B is high, etching resistance may be reduced due to the organic component in the etching process for forming the resist pattern. When the heat treatment temperature is increased or the heat treatment time is increased to decrease the content of organic components in the hard mask layer 20B, cracks may occur in the hard mask layer 20B due to applied thermal stress. In addition, as the substrate 10 such as a silicon wafer shrinks due to the heat treatment, the production yield of the semiconductor device may decrease.

Accordingly, in the present invention, laser light is irradiated to the composition for forming a hard mask after the coating process 20A or the preliminary hard mask film 20B after the heat treatment process. 4, since the metal-oxo bond among the metal-containing compounds included in the finally formed hardmask film 20 has a relatively high binding energy, the metal-oxo bond is not dissociated by laser irradiation. maintain. On the other hand, since the carbon-carbon bond, the carbon-hydrogen bond, and/or the metal-carbon bond constituting the ligand, which is an organic group in the metal-containing compound, have a relatively low binding energy, these bonds are dissociated by laser irradiation. As the carbon-carbon bond, the carbon-hydrogen bond, and the metal-carbon bond dissociate, the oxo group is bonded to the metal component in place of these dissociated bonds.

Accordingly, compared with the composition of the preliminary hardmask film 20B manufactured after the heat treatment process, the content of the metal component and/or the content of the oxygen component is relatively higher in the hardmask film 20 finally formed after laser irradiation. increases, and the content of the carbon component, which is an organic component, decreases. Since the content of the organic component having poor etch resistance is reduced, the etch resistance of the hardmask film 20 manufactured through the laser irradiation process is improved. Accordingly, when forming the resist pattern, it is possible to minimize the unevenness of the pattern. In addition, since laser light is irradiated, thermal stress applied to components constituting the hardmask film 20 can be minimized, and cracks can be prevented from occurring in the hardmask film 20 .

In an exemplary aspect, compared with the metal content in the cured product of the metal-containing compound having the structure of Formula 1 present in the preliminary hardmask film 20B after performing the heat treatment, the hardmask film 20 after laser irradiation The metal content in the cured product of the metal-containing compound present in the compound may be increased by 5 to 70%.

In an exemplary aspect, the wavelength of the laser irradiated to the composition for forming a hard mask ( 20A) or the preliminary hard mask film ( 20B) is 10 to 700 nm, for example, to form the finally manufactured hard mask film ( 20 ). For example, it may be 10-400 nm, or 13-350 nm.

For example, the laser may be a short-wavelength laser selected from the group consisting of an ion laser, a molecular laser, an excimer laser, and combinations thereof. A short-wavelength laser is a laser having a wavelength of 400 nm or less in an ultraviolet region and a vacuum ultraviolet region. More specifically, the light source used in the ion laser may be HeCd ⁺ (325 nm, 442 nm), Ar ²⁺ (351 nm), Kr ²⁺ (351 nm), Kr ³⁺ (195 nm), and combinations thereof. . The light source used in the molecular laser may be N ₂ (337 nm), H ₂ (a number in the range of 125-165, 110-127 nm), and combinations thereof. The light sources used in excimer lasers are Xe ₂ ^* (176 nm), Kr ₂ ^* (146 nm), Ar _z ^* (126 nm), XeF ^* (352 nm), KrF ^* (249 nm) ( ^* indicates the excited state. shown) and combinations thereof. In an exemplary aspect, the laser may be an excimer laser.

In an optional aspect, in the step of irradiating a laser, the laser emits 10 to 5000 mW per cm 2 , for example, 10 to 1000 mW per cm 2 , 10 to 500 mW per cm 2 , 10 to 100 mW per cm 2 , 20 per cm 2 to 70 mW or 20 to 50 mW per cm 2 may be irradiated.

The laser may be irradiated for 1 minute to 10 minutes, for example 1 minute to 5 minutes or 2 minutes to 5 minutes, and the step of irradiating the laser may be performed 1 to 10 times, for example 1 to 5 times. In addition, the light source irradiating the laser may be irradiated at a distance of 1 to 250 mm, for example, 10 to 100 mm from the hard mask forming composition 20A or the preliminary hard mask film 20B, but limited thereto. doesn't happen When the laser irradiation wavelength, laser irradiation intensity, laser irradiation time, number of laser irradiation and/or the separation distance of the laser light source meet the above-mentioned ranges, the etch resistance of the finally manufactured hardmask film 20 is improved, The occurrence of cracks can be minimized.

[Resist pattern formation method]

A method of forming a resist pattern using the above-described hard mask film forming method will be described. 5 to 7 are views schematically showing cross-sections of a substrate, a hardmask film, an interlayer film, and a resist film in the process of forming a resist pattern using a hardmask film containing a metal compound according to the present invention.

As shown in FIG. 5 , an intermediate layer film 30 is selectively formed on the hardmask film 20 , and a resist film 40 is formed on the intermediate layer film 30 . In an exemplary aspect, the interlayer film 30 may be a bottom anti-reflective coating (BARC). The lower anti-reflection film used as the interlayer film 30 may be made of an organic material or an inorganic material having a good extinction coefficient and refractive index. For example, the interlayer film 30 may be made of a material selected from the group consisting of titanium nitride, titanium oxynitride, silicon oxide, silicon oxynitride, silicon nitride, an amorphous carbon-based material, and combinations thereof. there is. The interlayer film 30 may be disposed on the hardmask film 20 through a deposition process or a coating process. For example, when the interlayer film 30 is made of an inorganic material, the interlayer film 30 may be formed using a chemical vapor deposition (CVD) method. The thickness of the interlayer film 30 may be 2 to 5000 nm, for example, 10 to 2000 nm, and the deposition temperature in chemical vapor deposition (CVD) may be 240 to 800° C., but is not limited thereto.

The hardmask film 20 in which the metal-containing compound having the structure of Formula 1 is cured has high thermal stability after laser irradiation. Accordingly, even when the interlayer film 30 made of an inorganic material is formed, the hardmask film 20 as a resist underlayer film containing a cured product of a metal-containing compound is not thermally-decomposed. That is, it is possible to prevent the inside of the equipment from being contaminated by the decomposition of the resist underlayer in the intermediate layer film 30 forming process performed at a high temperature. In addition, as organic components such as carbon and hydrogen that may remain in the hardmask film 20 are vaporized in this process, the etch resistance of the hardmask film 20 may be maximized. The interlayer film 30 may be formed as a single layer, or may have two or more multilayer structures made of the same or different materials.

A resist film 40 is formed on the hard mask film 20 or the intermediate layer film 30 . A photoresist material for forming the resist film 30 is well known, and the photoresist may be a negative type resist or a positive type resist. In an exemplary aspect, the photoresist material is a substituted polyhydroxystyrene and copolymer/onium salt system thereof, a polymer comprising an alicyclic hydrocarbon, a polymer obtained by radical polymerization of maleic anhydride and an unsaturated cyclic monomer, a pendant fluoro fluorinated polymers having alcohol groups, polymers having fluorinated-norbornene groups and copolymers of these polymers with tetrafluorethylene, cyclized polymers of asymmetric dienes, copolymers of fluorodiene and olefins, and combinations thereof However, it is not limited thereto.

Subsequently, as shown in FIG. 6 , the resist film 40 may be exposed according to a predetermined pattern to form a patterned resist film 40P. Exemplary exposure processes include excimer lasers, for example ArF excimer lasers with a wavelength of 193 nm, KrF excimer lasers, EUV, deep ultraviolet, ultraviolet, visible light, electron beam, X-ray or g-ray (wavelength 436 nm), h It can be carried out by irradiating -ray (wavelength 405 nm), i-ray (wavelength 365 nm), or a mixture thereof.

In order to smoothly perform the exposure process, exposure of a mask aligner, a stepper, and a scatterer on the resist film 40 formed on the hard mask film 20 or the intermediate layer film 30 on which the laser irradiation process is completed Appropriate light sources can be irradiated using equipment. For example, the exposure may be performed by a contact, proximity, or projection exposure method. The exposure energy may vary depending on the sensitivity of the prepared resist film, and an exposure energy of 10 to 300 mJ/cm ² , preferably 20 to 200 mJ/cm ² may be applied, but is not limited thereto.

After the exposure process is completed, the substrate 10 and the resist film 40 on which the hardmask film 20, optionally the interlayer film 30 are formed, are immersed in an appropriate developer or sprayed onto the substrate 10 ( spray) to remove the resist film 40 in the exposed portion or the non-exposed portion, thereby obtaining a patterned resist film 40P. For example, the developer may use 0.01 to 5% (w/v) tetramethylammonium hydroxide (TMAH) aqueous solution.

Subsequently, as shown in FIG. 7 , the interlayer film is selectively etched using the patterned resist film 40P as a mask to form a patterned interlayer film 30P, and the patterned resist film 40P or patterned resist film 40P A patterned hardmask film 20P is formed using the patterned interlayer film 30P as a mask, and a fine patterned substrate 10P is formed using the patterned hardmask film 20P as a mask. can

For example, the etching process for forming the patterned film may be a plasma etching process using CF ₄ or CHF ₃ gas, a plasma etching process using N ₂ and O ₂ gas, Cl ₂ or Plasma etching processes using BCl ₃ gas may be sequentially performed, and a wet cleaning process may be added in the middle. The pattern is sequentially transferred to the lower layer to make a pattern of the metal-containing hard mask layer 20P, and then a patterned substrate 10P is formed through an appropriate etching process.

In an exemplary aspect, etching to form a patterned interlayer film 30P, a patterned hardmask film 20P, and/or a patterned substrate 10P, based on the patterned resist film 40P The process may be performed under a gas atmosphere consisting of nitrogen, hydrogen, oxygen, helium, neo, argon, and combinations thereof. The etching process may be performed by a plasma etching process, and may be performed using a halogenated gas. For example, the halogenation gas may be performed using a gas consisting of CHF ₃ , CF _{4 ,} BCl ₃ , Cl ₂ , SF ₆ , nitrogen, oxygen, argon, and combinations thereof.

Hereinafter, the present invention will be described with reference to exemplary embodiments, but the present invention is not limited to the technical ideas described in the following examples.

Synthesis Example 1: Preparation of a composition for forming a metal-containing hard mask

The metal-containing compound Zr ₂ C ₁₈ H ₃₂ O ₁₀ (2.0 g, 3.39 mmol) and the compound for thickness enhancement indicated below (0.2 g, weight average molecular weight 1523) were added to propylene glycol monomethyl ether (PGMEA, 7.8 g). A composition for forming a hard mask was prepared. The composition for forming a hard mask was stirred at a temperature of 25° C. for 24 hours to dissolve both the metal-containing compound and the compound for thickness enhancement, and then passed through a polytetrafluoroethylene (pTFE) filter to finally form a metal-containing hard mask A composition was prepared.

[Thickness enhancement compound]

Synthesis Example 2: Preparation of a composition for forming a metal-containing hard mask

As a metal-containing compound, Ti ₄ C ₃₆ H ₆₄ O ₂₀ (2 g, 1.98 mmol) was used instead of Zr ₂ C ₁₈ H ₃₂ O ₁₀ , and the compound for thickness enhancement (0.2 g, weight average molecular weight 1523) was used. Except that, the same procedure as in Synthesis Example 1 was repeated to prepare a composition for forming a metal-containing hard mask.

Synthesis Example 3: Preparation of a composition for forming a metal-containing hard mask

Zr ₂ Al ₁ C ₂₇ H ₅₃ O ₁₃ (2.5 g, 3.14 mmol) was used in place of Zr ₂ C ₁₈ H ₃₂ O ₁₀ as the metal-containing compound, and except that the compound for enhancing the thickness was not used, The same procedure as in Synthesis Example 1 was repeated to prepare a composition for forming a metal-containing hard mask.

Synthesis Example 4: Preparation of a composition for forming a metal-containing hard mask

Zr ₂ Al ₁ C ₂₇ H ₅₃ O ₁₃ (2 g, 2.51 mmol) was used as a metal-containing compound instead of Zr ₂ C ₁₈ H ₃₂ O ₁₀ , and the compound for thickness enhancement (0.2 g, weight average molecular weight 1523) A composition for forming a metal-containing hard mask was prepared by repeating the same procedure as in Synthesis Example 1, except that .

Synthesis Example 5: Preparation of a composition for forming a metal-containing hard mask

As a metal-containing compound, Hf ₃ B ₁ C ₂₇ H ₅₃ O ₁₃ (1.9 g, 1.68 mmol) was used in place of Zr ₂ C ₁₈ H ₃₂ O ₁₀ , and the compound for thickness enhancement (0.2 g, weight average molecular weight 1523) A composition for forming a metal-containing hard mask was prepared by repeating the same procedure as in Synthesis Example 1, except that .

Synthesis Example 6: Preparation of a composition for forming a metal-containing hard mask

Synthesis Example 1, except that InSn ₃ C ₂₈ H ₆₅ O ₃ (2.4 g, 2.17 mmol) was used instead of Zr ₂ C ₁₈ H ₃₂ O ₁₀ as the metal-containing compound, and the compound for enhancing the thickness was not used. The same procedure was repeated to prepare a composition for forming a metal-containing hard mask.

Synthesis Example 7: Preparation of a composition for forming a metal-containing hard mask

As a metal-containing compound, InSn ₃ C ₂₈ H ₆₅ O ₃ (2.2 g, 2.39 mmol) was used instead of Zr ₂ C ₁₈ H ₃₂ O ₁₀ , and the compound for thickness enhancement (0.2 g, weight average molecular weight 1523) was used. Except that, the same procedure as in Synthesis Example 1 was repeated to prepare a composition for forming a metal-containing hard mask.

Synthesis Example 8: Preparation of a composition for forming a metal-containing hard mask

As a metal-containing compound, WC ₂₈ H ₆₀ O ₉ (1.88 g, 2.59 mmol) was used instead of Zr ₂ C ₁₈ H ₃₂ O ₁₀ , and the compound for thickness enhancement (0.22 g, weight average molecular weight 1523) was used except that and repeating the same procedure as in Synthesis Example 1 to prepare a composition for forming a metal-containing hard mask.

Table 1 below shows the type of the metal-containing compound added to the composition for forming a hard mask prepared in Synthesis Examples 1 to 8 and whether or not the thickness enhancing compound is added.

Composition of the composition for forming a hard mask Synthesis example metal-containing compounds Thickness enhancement compound One Zr ₂ C ₁₈ H ₃₂ O ₁₀ ○ 2 Ti ₄ C ₃₆ H ₆₄ O ₂₀ ○ 3 Zr ₂ Al ₁ C ₂₇ H ₅₃ O ₁₃ X 4 Zr ₂ Al ₁ C ₂₇ H ₅₃ O ₁₃ ○ 5 Hf ₃ B ₁ C ₂₇ H ₅₃ O ₁₃ ○ 6 InSn ₃ C ₂₈ H ₆₅ O ₃ X 7 InSn ₃ C ₂₈ H ₆₅ O ₃ ○ 8 WC ₂₈ H ₆₀ O ₉ ○

Example 1: Preparation of hard mask film

On a silicon wafer, the composition for forming a metal-containing hard mask prepared in Synthesis Example 1 in Synthesis Example 1 was spin-coated to a thickness of 1500 Å, and after preliminary curing at 250° C. for 1 minute and 400° C. for 1 minute, respectively, sealing placed in the device. A Xe ₂ excimer laser light source (wavelength: 172 nm) was irradiated for 1 minute at a position 5 cm away from the pre-cured hardmask film while flowing a nitrogen/oxygen mixed gas of 99:1 ratio at a rate of 80 ml/min. did The intensity of the excimer laser light source was set to 50.0 mW per cm 2 .

Example 2: Preparation of hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 1, except that an ArF excimer laser light source (wavelength: 193 nm) was irradiated to the heat-treated hard mask film at an intensity of 44.5 mW per cm 2 instead of the Xe ₂ excimer laser light source did

Example 3: Hard mask film preparation

Xe2 Excimer laser light source (wavelength: 351 nm) was irradiated to the heat-treated hard mask film at an intensity of 25.5 mW per cm 2 in place of the Xe ₂ excimer laser light source, except that the laser irradiation time was changed to 5 minutes The same procedure as in 1 was repeated to prepare a hardmask film.

Comparative Example 1: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 1, except that the laser light source was not irradiated after the heat treatment.

Example 4: Preparation of hardmask film

A hard mask film was prepared by repeating the same procedure as in Example 1, except that the composition for forming a metal-containing hard mask prepared in Synthesis Example 2 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1.

Comparative Example 2: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 4, except that the laser light source was not irradiated after the heat treatment.

Example 5: Preparation of hardmask film

The composition for forming a metal-containing hard mask prepared in Synthesis Example 3 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) in place of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 3: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 5, except that the laser light source was not irradiated after the heat treatment.

Example 6: Preparation of hardmask film

A hard mask film was prepared by repeating the same procedure as in Example 1, except that the composition for forming a metal-containing hard mask prepared in Synthesis Example 4 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1.

Example 7: Preparation of hardmask film

The composition for forming a metal-containing hard mask prepared in Synthesis Example 4 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) in place of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 4: Preparation of a hard mask film

A hard mask film was manufactured by repeating the same procedure as in Example 6, except that the laser light source was not irradiated after the heat treatment.

Example 8: Hardmask Film Preparation

The composition for forming a metal-containing hard mask prepared in Synthesis Example 5 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) was used instead of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 5: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 8, except that the laser light source was not irradiated after the heat treatment.

Example 9: Preparation of a hard mask film

The composition for forming a metal-containing hard mask prepared in Synthesis Example 6 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) was used instead of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 6: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 9, except that the laser light source was not irradiated after the heat treatment.

Example 10: Hardmask Film Preparation

The composition for forming a metal-containing hard mask prepared in Synthesis Example 7 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) was used instead of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 7: Preparation of a hard mask film

A hard mask film was prepared by repeating the same procedure as in Example 10, except that the laser light source was not irradiated after the heat treatment.

Example 11: Preparation of a hard mask film

The composition for forming a metal-containing hard mask prepared in Synthesis Example 8 was used instead of the composition for forming a metal-containing hard mask prepared in Synthesis Example 1, and an ArF excimer laser light source (wavelength: 193 nm) was used instead of the Xe ₂ excimer laser light source. ) was irradiated to the heat-treated hardmask film at an intensity of 44.5 mW per cm 2 , and the same procedure as in Example 1 was repeated to prepare a hardmask film.

Comparative Example 8: Preparation of hard mask film

A hard mask film was manufactured by repeating the same procedure as in Example 11, except that the laser light source was not irradiated after the heat treatment.

Experimental Example: Evaluation of the physical properties of the hard mask film

The etch resistance of the hardmask films prepared in Examples 1 to 11 and Comparative Examples 1 to 8, respectively, was evaluated, and the content of metal, carbon, and oxygen present in the hardmask film was measured using XPS equipment. Etching conditions are shown in Table 2 below.

Etching conditions enter
(mm Torr) Power CF ₄
(sccm) Ar
(sccm) O ₂
(sccm) time
(s)
40 27 MHz;
RF Power
(700 W) 2 MHz,
RF Power
(700 W)
42
600
15
30

As the etching equipment, Tel's SCCM model was used. The thickness before and after etching was measured with an ellipsometer to measure the thickness reduction, and the etch rate per second was obtained. The ellipsometer used J.A. Woollam's M2000D model. The metal content was measured by X-ray photoelectron analysis (XPS) of the film, and the weight ratio (wt%) of the metal was compared. As the XPS instrument, Kratos Analytical's AXIS Supra model was used. When there are two types of metal, the weight ratio of the sum of the two types was calculated. Since no hydrogen component was detected in XPS analysis, the contents of metal, oxygen and carbon components were analyzed. In addition, the thickness of the hard mask film was measured before and after the laser treatment, respectively, and the thickness reduction rate was measured according to the following equation.

Thickness reduction rate (%) = (1 - thickness of hard mask film after laser treatment / thickness before laser treatment) x 100

The etch rate, XPS analysis result, and thickness reduction rate for each hardmask film are shown in Table 3 below. As shown in Table 3 below, as compared to the hardmask film not irradiated with laser in Comparative Examples 1 to 8, the etching rate of the hardmask film irradiated with laser in Examples 1 to 11 was decreased, so that the etching resistance was improved. improved In addition, as compared with the hardmask film prepared in Comparative Example, the content of the metal component was increased in the hardmask film prepared in Example, and the content of the carbon component constituting the organic ligand was decreased. In addition, the thickness of the hardmask film hardly decreased even by laser irradiation.

Hard mask film properties evaluation Sample hard mask composition laser
(wavelength, nm) etch rate
(Å/s) XPS (wt%) thickness
decrease rate Comparative Example 1 Synthesis Example 1 - 26.9 Zr: 16%, C: 44%, O: 41% - Example 1 Synthesis Example 1 Xe ₂ (172) 20.8 Zr: 22%, C: 31%, O: 46% 3.9% Example 2 Synthesis Example 1 ArF (193) 21.3 Zr: 22%, C: 32%, O: 46% 2.0% Example 3 Synthesis Example 1 XeF (351) 24.4 Zr: 17%, C: 39%, O: 43% 0.8% Comparative Example 2 Synthesis Example 2 - 27.8 Ti: 19%, C: 41%, O: 39% - Example 4 Synthesis Example 2 Xe ₂ (172) 22.8 Ti: 23%, C: 34%, O: 43% 7.1% Comparative Example 3 Synthesis Example 3 - 21.6 Zr: 19%, Al: 2%, C: 39%, O: 39% - Example 5 Synthesis Example 3 ArF (193) 16.9 Zr: 23%, Al: 2%, C: 32%, O: 42% 2.3% Comparative Example 4 Synthesis Example 4 - 25.4% Zr: 16%, Al: 1%, C: 47%, O: 34% - Example 6 Synthesis Example 4 Xe ₂ (172) 19.8% Zr: 19%, Al: 2%, C: 39%, O:39% 3.1% Example 7 Synthesis Example 4 ArF (193) 19.9% Zr: 19%, Al: 2%, C: 39%, O: 39% 2.5% Comparative Example 5 Synthesis Example 5 - 21.3 Hf: 17%, B: 1%, C: 41%, O: 40% - Example 8 Synthesis Example 5 ArF (193) 17.5 Hf: 19%, B: 2%, C: 39%, O: 39% 2.1% Comparative Example 6 Synthesis Example 6 - 31.3 In: 3.5%, Sn: 11.5%, C: 41%, O: 43% - Example 9 Synthesis Example 6 ArF (193) 28.8 In: 4%, Sn: 15%, C: 38%, O: 41% 3.1% Comparative Example 7 Synthesis Example 7 - 35.4 In: 2.5%, Sn: 8.5%, C: 48%, O: 38% - Example 10 Synthesis Example 7 ArF (193) 29.9 In: 4%, Sn: 12%, C: 42%, O: 42% 2.8% Comparative Example 8 Synthesis Example 8 - 27.3 W: 9%, C: 51%, O: 40% - Example 11 Synthesis Example 8 ArF (193) 22.5 W: 15%, C: 44%, O: 41% 4.4%

In the above, the present invention has been described based on exemplary embodiments and examples of the present invention, but the present invention is not limited to the technical ideas described in the above embodiments and examples. Rather, those of ordinary skill in the art to which the present invention pertains can easily propose various modifications and changes based on the above-described embodiments and examples. However, it is clear from the appended claims that all such modifications and changes fall within the scope of the present invention.

10, 10P: substrate
20, 20B, 20P: hard mask film
20A: composition for forming a hard mask
30, 30P: interlayer film
40, 40P: resist film

Claims (29)

Coating a composition for forming a hard mask including a metal-containing compound having a structure of Formula 1 below, an organic solvent, and a compound for enhancing thickness on a substrate;
Irradiating a laser to the composition for forming a hard mask so that the metal-containing compound is cured to form a hard mask film
A method for producing a metal-containing hard mask film comprising a.
[Formula 1]

In Formula 1, M ¹ is a metal of Groups 3 to 16 of the Periodic Table; M ² is selected from the group consisting of metals of Groups 3 to 16 of the periodic table, C, Si, B, P and S; R is hydrogen or a C ₁ -C ₃₀ hydrocarbyl group; L ¹ and L ² are each independently a ligand selected from Formula 2 below; A is a linking group having a structure of Formula 4, Formula 5, or Formula 6; m is an integer from 1 to 100; n is an integer from 0 to 100; p and q are each independently an integer from 0 to 6.
[Formula 2]

In Formula 2, R ¹ to R ⁴ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ¹ ; M ³ is selected from the group consisting of Li, Si, B, P, S and a metal of Groups 3 to 16 of the periodic table; L ₃ is a ligand selected from the following formula (3); r is an integer from 0 to 6; An asterisk indicates a site connected to M ¹ or M ² in Formula 1; Q ¹ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
[Formula 3]

In Formula 3, R ¹¹ to R ¹³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of a heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ² ; An asterisk indicates a site connected to M ³ of Formula 2; Q ² is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
[Formula 4]

[Formula 5]

[Formula 6]

In Formula 4, L ⁴ and L ⁵ are each independently a C ₁ -C ₂₀ alkylene group, a C ₂ -C ₂₀ alkylene group having a carbon-carbon double bond, a C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond, C ₃ -C ₂₀ cycloalkylene group, C ₆ -C ₃₀ arylene group, C ₃ -C ₃₀ hetero arylene group, the C ₁ -C ₂₀ alkylene group, C ₂ -C ₂₀ alkyl having a carbon-carbon double bond The ene group and the C ₂ -C ₂₀ alkylene group having a carbon-carbon triple bond may each independently be unsubstituted or substituted with at least one Q ³ ; D is a direct bond, NR ¹⁴ , O or S, and R ¹⁴ is a hydrogen atom, a hydroxy group, a C ₁ -C ₁₀ alkyl group, a C ₆ -C ₂₀ aryl group or a C ₃ -C ₂₀ heteroaryl group; Q ³ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
In Formula 5, R ²¹ and R ²² are each independently selected from the group consisting of a hydrogen atom, a C ₁ -C ₁₀ alkyl group, and a C ₆ -C ₂₀ aryl group; s is an integer from 1 to 1000.
In Formula 6, M ⁴ is selected from the group consisting of Li, C, Si, B, P, S, and metals of Groups 3 to 16 of the periodic table; L ⁶ is a hydrogen atom, a halogen atom, =O, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group , C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ It is selected from the group consisting of a heteroaryl alkyl group and a ligand having a structure of Formula 7 below, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, the C ₂ -C ₂₀ alkynyl group, and the C ₁ - each C ₂₀ alkoxy group may be independently unsubstituted or substituted with at least one Q ⁴ ; t is an integer from 0 to 6; Q ⁴ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group; In Formulas 4 to 6, an asterisk represents a connection site, respectively.
[Formula 7]

In Formula 7, R ³¹ to R ³³ are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₃ - C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ selected from the group consisting of heteroaryl alkyl group, the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, and the C ₁ -C ₂₀ alkoxy group are each independently may be unsubstituted or substituted with at least one Q ⁵ ; An asterisk indicates a site connected to M ⁴ in formula (6); Q ⁵ is selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
The method of claim 1,
The wavelength of the laser is 10 to 700 nm.
The method of claim 1,
The wavelength of the laser is 10 to 400 nm.
The method of claim 1,
The laser is selected from the group consisting of an ion laser, a molecular laser, an excimer laser, and combinations thereof.
The method of claim 1,
wherein the laser comprises an excimer laser.
The method of claim 1,
The content of the metal component in the metal-containing compound is 5 to 70% by weight.
7. The method of claim 6,
In the metal-containing compound, the content of carbon is 10 to 60% by weight, the content of oxygen is 10 to 60% by weight, and the remaining amount of hydrogen is included.
The method of claim 1,
In the step of irradiating the laser, the laser is irradiated at an intensity of 10 to 5000 mW per cm 2 .
The method of claim 1,
The step of irradiating the laser is performed for 1 minute to 10 minutes.
The method of claim 1,
The step of irradiating the laser is performed 1 to 10 times.
The method of claim 1,
In the step of irradiating the laser, the light source irradiating the laser is irradiated at a distance of 1 to 250 mm from the composition for forming the hard mask.
The method of claim 1,
The method further comprising the step of performing a heat treatment on the composition for forming the hard mask between the coating step and the step of irradiating the laser.
13. The method of claim 12,
Compared with the metal content in the cured product of the metal-containing compound having the structure of Formula 1 present in the hardmask film after performing the heat treatment, the amount of the metal-containing compound present in the hardmask film after irradiating the laser A method wherein the metal content in the cured product is increased by 5 to 70%.
13. The method of claim 12,
The heat treatment is performed at 150 to 500 ℃ for 30 seconds to 10 minutes.
delete delete The method of claim 1,
The thickness enhancement compound includes an organic compound having a repeating structure of the following formula (8).
[Formula 8]

In Formula 8, R ⁴¹ and R ⁴² are each independently a hydrogen atom, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ heteroaryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ heteroaryl alkyl group and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group, and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁶ ; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₃ -C ₃₀ hetero aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ hetero aryl oxy group, C ₇ -C ₃₀ aryl alkyl group and C ₄ -C ₃₀ hetero It is selected from the group consisting of an aryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or substituted with at least one Q ⁷ . has exist; L ⁷ is a linking group selected from the following formula (9); B is selected from the following formula (10); Q ⁶ and Q ⁷ are each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
[Formula 9]

[Formula 10]

In Formula 9, Y is each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, a carboxy group, a nitro group, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, Amino group, C ₁ -C ₂₀ alkyl amino group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₃₀ aryl group, C ₆ -C ₃₀ aryloxy group, C ₃ -C ₃₀ heteroaryloxy group, C ₇ -C ₃₀ It is selected from the group consisting of an aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, and the C ₁ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group are each independently unsubstituted or may be substituted with at least one Q ⁸ ; Q ⁸ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
In Formula 10, each Z is independently a hydrogen atom, a halogen atom, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group, and a C ₆ -C ₃₀ selected from the group consisting of an aryl group, a C ₆ -C ₃₀ aryloxy group, a C ₃ -C ₃₀ heteroaryloxy group, a C ₇ -C ₃₀ aryl alkyl group and a C ₄ -C ₃₀ heteroaryl alkyl group, wherein the C ₁ - The C ₂₀ alkyl group, the C ₂ -C ₂₀ alkenyl group and the C ₁ -C ₂₀ alkoxy group may each independently be unsubstituted or substituted with at least one Q ⁹ ; Q ⁹ is each independently selected from the group consisting of a ketone group, an aldehyde group, an ester group, and a carboxy group.
In Formulas 9 and 10, an asterisk indicates a connection site.
The method of claim 1,
In the composition for forming a hard mask, the thickness enhancing compound is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the metal-containing compound having the structure of Formula 1 above.
The method of claim 1,
The step of coating the composition for forming the hard mask is selected from the group consisting of spin coating, slot die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, bar coating, slit coating, and combinations thereof. how to be
20. A method comprising: forming a resist film on the hard mask film produced by the method according to any one of claims 1 to 14 and 17 to 19;
exposing the resist film; and
Developing the exposed resist film to form a patterned resist film
A method of forming a resist pattern comprising a.
21. The method of claim 20,
After forming the patterned resist film, etching the hardmask film based on the patterned resist film to form a patterned hardmask film, and etching the substrate based on the patterned hardmask film to form a pattern The method further comprising the step of forming a textured substrate.
22. The method of claim 21,
In the step of forming the patterned hardmask layer, the etching process is performed under a gas atmosphere consisting of nitrogen, hydrogen, oxygen, helium, neo, argon, and combinations thereof.
22. The method of claim 21,
In the step of forming the patterned hardmask layer, the etching process is performed by a plasma etching process.
22. The method of claim 21,
In the step of forming the patterned hardmask layer, the etching treatment is performed using a gas consisting of CHF ₃ , CF _{4 ,} BCl ₃ , Cl ₂ , SF ₆ , nitrogen, oxygen, argon, and combinations thereof.
21. The method of claim 20,
The method further comprising the step of forming an interlayer film on the hardmask film before the step of forming the resist film.
26. The method of claim 25,
After forming the patterned resist film, etching the interlayer film based on the patterned resist film to form a patterned interlayer film, and etching the hardmask film based on the patterned interlayer film to form a patterned interlayer film. A method further comprising: forming a hardmask film; and etching the substrate based on the patterned hardmask film to form a patterned substrate.
26. The method of claim 25,
wherein the interlayer film includes a lower anti-reflection film.
26. The method of claim 25,
wherein the interlayer film is made of a material selected from the group consisting of titanium nitride, titanium oxynitride, silicon oxide, silicon oxynitride, silicon nitride, an amorphous carbon-based material, and combinations thereof.
A semiconductor device manufactured through the pattern forming method according to claim 20.

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