KR102632885B1 - Fluorene-based organic compound, organic film having thereof and application thereof - Google Patents

Abstract

The present invention relates to a fluorene-based organic compound having the structure of the following formula (1), a composition for forming an organic film using the same, an organic film, a method for manufacturing an organic film, a method for forming a pattern, and a semiconductor device. By introducing the underlayer film obtained from the fluorene-based organic compound synthesized according to the present invention, a photoresist pattern with excellent resist pattern characteristics and coating characteristics can be formed, thereby realizing a fine semiconductor device.
[Formula 1]

Description

Fluorene-based organic compounds, organic films containing them, and applications {FLUORENE-BASED ORGANIC COMPOUND, ORGANIC FILM HAVING THEREOF AND APPLICATION THEREOF}

This patent application is a research result supported by the "Development of 2um thick spin coating hard mask material for memory semiconductor exposure process" project (Project number: S2829770, Host organization: DCTM Material) of the Ministry of SMEs and Startups of the Government of the Republic of Korea. .

The present invention relates to organic compounds, and more specifically, to fluorene-based organic compounds that can be applied to resist underlayer films, organic films containing them, and industrial applications and uses in semiconductor device processes.

Semiconductor devices, including memory devices required in the process of manufacturing semiconductors, are gradually becoming smaller and more highly integrated. As semiconductor devices become more highly integrated, finer patterns must be formed when manufacturing semiconductor devices compared to conventional semiconductor device patterns. In the photo lithography process using a light source, which is currently used as a general-purpose technology in semiconductor pattern manufacturing, the intrinsic resolution limit derived from the wavelength of the light source is approaching.

As light sources used in the photolithography process used to form resist patterns, g-line (436nm) and i-line (365nm) using mercury lamps are widely used, and to refine the pattern, a KrF excimer laser (excimer The photolithography process is performed mainly using short-wavelength light sources such as laser (248 nm) and ArF excimer laser (193 nm). Recently, a photolithography process using EUV (Extreme Ultraviolet) in the shorter wavelength 13.5 nm wavelength range as a light source is in the commercialization stage, and many research and development efforts are being attempted to solve problems arising from processes using such ultra-short wavelength light sources. .

When using an ArF excimer laser light source, which is currently widely used in the photolithography process for forming patterns in semiconductor devices, there is a limit to the intrinsic resolution derived from the unique wavelength of the light source. As a method to overcome this and form finer patterns, double patterning technology is used to realize ultra-fine patterns by repeating the photolithography process twice, and double patterning technology is used to obtain patterns with the desired resolution by performing the exposure process twice. After performing the double expose patterning technology or the exposure process once, a spacer is formed on the sacrificial layer pattern using Chemical Vapor Deposition (CVD) and the sacrificial layer is removed. Spacer patterning technology has been proposed to obtain patterns with desired resolution, and is currently being applied to the mass production process of semiconductor devices.

However, it is not possible to directly etch a semiconductor substrate such as a silicon wafer using a fine photoresist pattern. Therefore, an underlayer film process is generally applied in which a resist underlayer or hard mask film is introduced between the resist film and the semiconductor substrate, the underlayer film or hard mask film is patterned, and then the substrate is etched.

The resist _underlayer is made of inorganic materials, such as silicon nitride (SiN _x ), silicon oxynitride ( _SiO It is formed by the (chemical vapor deposition: CVD) method.

The resist underlayer made of inorganic material produced by chemical vapor deposition has excellent etch selectivity and etch resistance. However, since the inorganic material forms a resist underlayer film through a deposition process, the lower step is directly reflected in the underlayer film. In addition, when forming a resist underlayer using an inorganic material, voids are generated due to pattern miniaturization, making it difficult to proceed with the planarization process. In addition, forming a resist underlayer using an inorganic material requires expensive equipment such as a vacuum deposition device, which has the disadvantage of high initial investment cost and low productivity of the process.

An object of the present invention is to provide a fluorene-based organic compound having high thermal stability and excellent gap fill properties and planarization characteristics, a composition for forming an organic film comprising the fluorene-based organic compound, and the fluorene-based organic compound. The object is to provide an organic film obtained from a compound, a method for manufacturing an organic film, and a method for forming a resist pattern for manufacturing a semiconductor device using the same.

Another object of the present invention is to provide a fluorene-based organic compound that can be produced without introducing expensive deposition equipment, a composition for forming an organic film containing the fluorene-based organic compound, and an organic film obtained from the fluorene-based organic compound. The object is to provide a method for manufacturing a film and an organic film, and a method for forming a resist pattern for manufacturing a semiconductor device using the same.

According to one aspect, a fluorene-based organic compound having the structure of Formula 1 below is disclosed.

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently hydrogen, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkylamino group, C ₄ to C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C ₃₀ heteroaryl group, C ₃ ~ C ₃₀ heteroaryloxy group or C ₃ to C ₃₀ heteroarylamino group, and the C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkyl amino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocycloalkyl group, C ₆ ~C ₃₀ aryl group, C 6 ~C ₃₀ aryloxy group, C _{6 ~} C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C ₃ ~ C ₃₀ heteroaryloxy group and C ₃ ~ C ₃₀ heteroarylamino group are each independently a halogen atom, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocycloalkyl group, _{C 6} ~C ₃₀ aryl group, C 6 ~C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C may be further substituted with at least one other functional group consisting of a ₃ to C ₃₀ heteroaryloxy group and a C ₃ to C ₃₀ heteroaryl amino group; Each R ¹ may be different or the same; p is the number of substituents other than hydrogen and is an integer of 0 to 10, q is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same, and q When there is a plurality, each R ³ may be different or the same; Each Z is independently ^* =X or ^* -Y (asterisks indicate linkages), and each Z may be different or the same; ^{Each of} _{_ _ _ _ _ _ _ _} Alkyl amino group, C ₄ ~ C ₂₀ cyclo alkyl group, C ₃ ~ C ₂₀ heterocyclo alkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C ₃₀ heteroaryl group, C ₃ to C ₃₀ heteroaryloxy group or C ₃ to C ₃₀ heteroaryl amino group, and the C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ ~C ₂₀ alkyl amino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocyclo alkyl group, C ₆ ~C ₃₀ aryl group, C ₆ ~C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C ₃ ~C ₃₀ heteroaryloxy group, and C ₃ ~C ₃₀ heteroaryl amino group are each independently a halogen atom, C ₁ ~C ₂₀ alkyl group, C ₁ ~C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamino group, C ₄ ~ C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ may be further substituted with at least one other functional group consisting of a C ₃₀ heteroaryl group, a C ₃ to C ₃₀ heteroaryloxy group and a C ₃ to C ₃₀ hetero aryl amino group; Y is each independently hydroxy group, amino group, thiol group, amino hydroxy group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amino group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl Amino group, C ₃ ~ C ₃₀ heteroaryloxy group or C ₃ ~ C ₃₀ heteroaryl amino group, and the C 1 ~ C ₂₀ alkoxy group, C _{1 ~} C ₂₀ alkyl amino group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryloxy group, and C ₃ ~C ₃₀ heteroaryl amino group are each independently a halogen atom, C ₁ ~C ₂₀ alkyl group, C ₁ ~C ₂₀ alkoxy group, C ₁ ~C ₂₀ alkylamino group, C ₄ ~ C ₂₀ cyclo alkyl group, C ₃ ~ C ₂₀ heterocyclo alkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C It may be further substituted with at least one other functional group consisting of _{a 30} heteroaryl group, a C ₃ -C ₃₀ heteroaryloxy group, and a C ₃ -C ₃₀ heteroaryl amino group.

As an example, the fluorene-based organic compound may have the structure of Formula 2 below.

[Formula 2]

In Formula 2, R ¹ to R ³ , Z and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

In an exemplary aspect, the fluorene-based organic compound may have the structure of Formula 3 below.

[Formula 3]

In Formula 3, R ¹ to R ³ , X and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

In an optional aspect, the fluorene-based organic compound may have the structure of Formula 4 below.

[Formula 4]

In Formula 4, R ¹ to R ³ , Y and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

For example, in Formula 1, R ¹ is hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryloxy group, or a C ₆ to C ₂₀ aryl amino group, and the C ₆ to C ₂₀ aryl group, C ₆ ~C ₂₀ aryloxy group, and C ₆ ~C ₂₀ aryl amino group are each independently composed of a C ₁ -C ₁₀ alkyl group, a C ₆ ~C ₂₀ aryl group, and a C ₃ ~C ₂₀ heteroaryl group. It may be further substituted with at least one other functional group, and R ² and R ³ are each independently hydrogen, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₁₀ alkenyl group, C ₁ ~ C ₁₀ alkoxy group, or C ₁ ~ C ₁₀ amino group, p and q are each independently integers of 0 to 2, X is NR ⁵ , O or S, R ⁵ is hydrogen, hydroxy group or C ₁ to C ₂₀ alkoxy group, and Y may be a hydroxy group or a C ₁ to C ₂₀ alkoxy group.

In another aspect, the fluorene-based organic compounds described above; and an organic solvent for dispersing the fluorene-based organic compound. A composition for forming an organic film is disclosed.

For example, the composition for forming an organic film may further include a polymer for enhancing film thickness.

For example, the weight average molecular weight (M _w ) of the film thickness enhancing polymer may be 2000 to 4000.

The content of the fluorene-based organic compound among the solid components excluding the organic solvent in the composition for forming an organic film may be at least 25% by weight.

In an exemplary aspect, the film thickness enhancing polymer may include at least one of a fluorene-based polymer having a repeating unit of Formula 5 below and a bisphenol-based polymer having a repeating unit of Formula 6 below.

[Formula 5]

[Formula 6]

In Formulas 5 and 6, A and B are each independently a C ₆ to C ₃₀ aromatic ring or a C ₃ to C ₃₀ heteroaromatic ring; R ¹¹ is each independently hydrogen, glycidyl group, C ₁ ~ C ₁₀ alkyl group, C ₂ ~ C ₁₀ alkenyl group, C ₄ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, or C ₃ ~ C ₂₀ heteroaryl appointment; R ¹² and R ¹³ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, a C ₄ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ heteroaryl group. ; L ₁ and L ₂ are each independently a single bond, an ether group, an ester group, a C ₁ to C ₁₀ alkylene group, a C ₆ to C ₂₀ arylene group, or a C ₃ to C ₂₀ hetero arylene group; m and n are each independently integers from 0 to 2, and when m and n are plural, each R ¹¹ and each R ¹² may be different or the same; q is the number of substituents other than hydrogen and is an integer from 0 to 4, and when q is plural, each R ¹³ may be different or the same.

In another aspect, an organic film comprising a cured product of the composition for forming an organic film described above is disclosed.

In another aspect, applying the composition for forming an organic film described above; and curing the composition for forming an organic film applied on the substrate.

In another aspect, applying the composition for forming an organic film described above; forming an underlayer film by curing the composition for forming an organic film applied on the substrate; forming a resist film on the underlayer film; performing an exposure process on the resist film; and forming a resist pattern by performing a development process on the exposed resist film.

For example, after forming the resist pattern, etching the lower layer using the resist pattern as a mask to obtain a patterned lower layer, and etching the substrate using the patterned lower layer as a mask. Thus, the step of forming a pattern on the substrate may be further included.

In an optional aspect, between forming the underlayer film and forming the resist film, forming an intermediate layer film on the underlayer film, and between forming the resist pattern and obtaining the patterned underlayer film. The method may further include forming a patterned intermediate layer film by etching the intermediate layer film using the resist pattern as a mask.

For example, the intermediate layer film may be made of an inorganic material selected from the group consisting of titanium nitride, titanium oxynitride, silicon oxide, silicon oxynitride, silicon nitride, and combinations thereof.

In another aspect, a semiconductor device manufactured through the above-described pattern forming method is disclosed.

In the fluorene-based organic compound of the present invention, two benzene rings connected to a fluorene moiety are each connected to an aromatic ring substituted with a predetermined functional group through multiple ether bonds. Fluorene-based compounds have excellent thermal stability and excellent gap filling and planarization properties.

An organic film with excellent physical properties can be created by coating one side of an appropriate substrate with a composition for forming an organic film containing the fluorene-based organic compound of the present invention alone or in combination with a film thickness enhancing polymer, and volatilizing the organic solvent. The organic film manufactured according to the present invention is not damaged even at a high temperature of 250 to 500° C. performed in the resist underlayer film process of a semiconductor device, and there is no uneven shape in the profile of the pattern formed after etching to form a resist pattern.

Therefore, the difficulty of the photoresist process for implementing a semiconductor micropattern can be greatly reduced by using the fluorene-based organic compound according to the present invention.

In addition, the composition for forming an organic film containing a fluorene-based organic compound according to the present invention has excellent fluidity. Therefore, it can be used as a composition material for forming an organic film with excellent gap filling and planarization properties by increasing flowability at the semiconductor processing temperature. For example, even when applied to substrates such as wafers with steps in a semiconductor photolithography process, an excellent organic film can be manufactured without the need for a separate planarization process by using the fluorene-based organic compound of the present invention. there is.

Accordingly, the composition for forming an organic film containing a fluorene-based organic compound synthesized according to the present invention is applied and cured on a substrate such as a semiconductor substrate, a photoresist having an appropriate pattern is formed, and then exposed to light. By performing a resist process through, a fine pattern can be easily formed on the substrate.

1 to 3 are graphs showing thermogravimetric analysis (TGA) results for an organic film formed on a silicon wafer according to an exemplary embodiment of the present invention, respectively.
4 and 5 are scanning electron microscope (SEM) photographs showing the results of evaluating the flatness characteristics of an organic film formed on a silicon wafer according to an exemplary embodiment of the present invention, respectively.
Figure 6 is an SEM photograph showing the results of evaluating the flatness characteristics of an organic film formed on a silicon wafer according to a comparative example.

Hereinafter, the present invention will be described with reference to the accompanying drawings where necessary.

[Fluorene-based organic compounds and production methods]

Instead of a resist underlayer made of an inorganic material using a conventional deposition method, a resist underlayer made of an organic material that can be solution processed does not use a deposition process, so the lower step can be alleviated and the voids within the pattern can be reduced. The occurrence is less than that of the inorganic underlayer film. In addition, the resist underlayer film made of organic material not only has excellent coating characteristics, but also has the advantage of reducing costs and providing excellent throughput because it does not require separate equipment during the photoresist process. However, the organic resist underlayer has a disadvantage in that the etch selectivity is lower than that of the inorganic resist underlayer.

The resist underlayer film of organic material formed between the substrate and the resist film is a hydrocarbon compound capable of an etching process using oxygen gas. The resist underlayer made of organic material must have high etching resistance because it must act as a hard mask when etching the substrate underneath, and for oxygen gas etching, it must be composed only of hydrocarbons that do not contain silicon atoms. there is.

The line width and height of the fine semiconductor pattern formed in this way are only about tens to hundreds of nanometers. Therefore, the organic material constituting the resist underlayer located between the substrate on which the fine semiconductor pattern is formed and the resist film is required to have gap fill characteristics so that it can effectively fill the space between patterns with high step differences. In addition to these etch resistance and gap fill characteristics, the resist underlayer controls the standing wave of the upper resist layer and prevents the collapse of fine patterns in an exposure process using a KrF and ArF light source or an EUV light source. To prevent this, it is necessary to also have the function of an anti-reflection film on the light source. For example, it is necessary to suppress the reflectance from the resist underlayer film to the resist film to 1% or less.

That is, when forming a resist pattern using a photolithography process to form a semiconductor pattern, a resist underlayer or hard mask film is used between the top of the substrate and the resist film. The resist underlayer or hard mask film made of organic material must be able to flatten the uneven shape of the substrate on which a predetermined fine pattern is to be formed through a photoresist process. In particular, organic materials that can be used as a resist underlayer or hard mask film have excellent gap fill and planarization characteristics, and decompose under high temperature conditions (e.g., 240 to 500°C) associated with the photoresist process. It must have sufficient high heat resistance to prevent heat dissipation.

In particular, if the substrate to be processed has an uneven shape formed in the process of forming a fine pattern such as a hole or trench, the inside of the pattern must be filled with an appropriate film without any voids to satisfy gap fill characteristics. . In addition, if there are steps in the substrate to be processed, or if an area with dense fine patterns and an area without a pattern exist on the same substrate, it is necessary to planarize the substrate surface using a hard mask film.

By flattening the surface of the hard mask film as a resist underlayer film, when forming an intermediate layer or resist film thereon, thickness variation depending on the area can be minimized, thereby creating a focus margin in the photolithography process or the subsequent mask film. Sufficient process margin of the processed substrate can be obtained.

In addition, when using a stacked structure to form a high-performance semiconductor pattern, the thickness of the resist underlayer used to make the through-type electrode can also become thick. In order to develop a resist film and transfer a resist pattern, the thickness of the hardmask film must be high, which allows selective etching, making it possible to etch a sufficiently deep pattern even with the minimum photoresist film thickness.

The fluorene-based organic compound according to the present invention can form an organic film with excellent heat resistance properties as well as gap fill properties and planarization properties. The fluorene-based organic compound of the present invention contains structures such as aromatic ether bonds and quaternary carbon bonds with strong bonding strength without loss of heat resistance. For example, the fluorene-based organic compound with improved physical properties such as heat resistance, gap fill, and planarization properties according to the present invention may have the structure of Formula 1 below.

[Formula 1]

In Formula 1, R ¹ to R ³ are each independently hydrogen, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkylamino group, C ₄ to C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C ₃₀ heteroaryl group, C ₃ ~ C ₃₀ heteroaryloxy group or C ₃ to C ₃₀ heteroarylamino group, and the C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkyl amino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocycloalkyl group, C ₆ ~C ₃₀ aryl group, C 6 ~C ₃₀ aryloxy group, C _{6 ~} C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C ₃ ~ C ₃₀ heteroaryloxy group and C ₃ ~ C ₃₀ heteroarylamino group are each independently a halogen atom, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocycloalkyl group, _{C 6} ~C ₃₀ aryl group, C 6 ~C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C may be further substituted with at least one other functional group consisting of a ₃ to C ₃₀ heteroaryloxy group and a C ₃ to C ₃₀ heteroaryl amino group; Each R ¹ may be different or the same; p is the number of substituents other than hydrogen and is an integer of 0 to 10, q is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same, and q When there is a plurality, each R ³ may be different or the same; Each Z ^is independently ^* = ^{Each of} _{_ _ _ _ _ _ _ _} Alkyl amino group, C ₄ ~ C ₂₀ cyclo alkyl group, C ₃ ~ C ₂₀ heterocyclo alkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C ₃₀ heteroaryl group, C ₃ to C ₃₀ heteroaryloxy group or C ₃ to C ₃₀ heteroaryl amino group, and the C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkoxy group, C ₁ ~C ₂₀ alkyl amino group, C ₄ ~C ₂₀ cycloalkyl group, C ₃ ~C ₂₀ heterocyclo alkyl group, C ₆ ~C ₃₀ aryl group, C ₆ ~C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryl group, C ₃ ~C ₃₀ heteroaryloxy group, and C ₃ ~C ₃₀ heteroaryl amino group are each independently a halogen atom, C ₁ ~C ₂₀ alkyl group, C ₁ ~C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamino group, C ₄ ~ C ₂₀ cycloalkyl group, C ₃ ~ C ₂₀ heterocycloalkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ may be further substituted with at least one other functional group consisting of a C ₃₀ heteroaryl group, a C ₃ to C ₃₀ heteroaryloxy group and a C ₃ to C ₃₀ heteroaryl amino group; Y is each independently hydroxy group, amino group, thiol group, amino hydroxy group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amino group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl Amino group, C ₃ ~ C ₃₀ heteroaryloxy group or C ₃ ~ C ₃₀ heteroaryl amino group, and the C 1 ~ C ₂₀ alkoxy group, C _{1 ~} C ₂₀ alkyl amino group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~C ₃₀ aryl amino group, C ₃ ~C ₃₀ heteroaryloxy group, and C ₃ ~C ₃₀ heteroaryl amino group are each independently a halogen atom, C ₁ ~C ₂₀ alkyl group, C ₁ ~C ₂₀ alkoxy group, C ₁ ~C ₂₀ alkylamino group, C ₄ ~ C ₂₀ cyclo alkyl group, C ₃ ~ C ₂₀ heterocyclo alkyl group, C ₆ ~ C ₃₀ aryl group, C ₆ ~ C ₃₀ aryloxy group, C ₆ ~ C ₃₀ aryl amino group, C ₃ ~ C It may be further substituted with at least one other functional group consisting of _{a 30} heteroaryl group, a C ₃ to C ₃₀ heteroaryloxy group and a C ₃ to C ₃₀ heteroaryl amino group.

In this specification, 'unsubstituted' means that the hydrogen atom is connected, and in this case, the hydrogen atom includes light hydrogen, deuterium, and tritium.

In one exemplary aspect, R ¹ of Formula 1 is hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryloxy group, or a C ₆ to C ₂₀ aryl amino group, C ₆ to C ₂₀ aryl group, C ₆ to C ₂₀ aryloxy group and C ₆ to C ₂₀ aryl amino group are each independently C ₁ -C ₁₀ alkyl group, C ₆ to C ₂₀ aryl group and C ₃ to C ₂₀ heteroaryl. may be further substituted with at least one other functional group consisting of a group, and R ² and R ³ are each independently hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, or a C ₁ to C ₁₀ alkoxy group, or C ₁ ~ C ₁₀ It is an amino group, p and q are each independently an integer of 0 to 2, X is NR ⁵ , O or S, R ⁵ is hydrogen, a hydroxy group or a C ₁ ~ C ₂₀ alkoxy group. , Y may be a hydroxy group or a C ₁ to C ₂₀ alkoxy group.

For example, in Formula 1, R ¹ is hydrogen; Substituents with chain structures such as methyl group, ethyl group, and methyl trifluoride group; C ₃ -C ₁₀ cycloalkyl groups such as cyclohexyl groups; C ₆ to C ₂₀ aryl group or C ₆ to C ₂₀ aryloxy such as phenyl group, naphthyl group, anthracenyl group, biphenyl group, pyrenyl group, triphenylenyl group, pentafluorophenyl group, phenoxyphenyl group, and methoxyphenyl group. It may be a group, and R ² and R ³ may each independently be hydrogen or a C ₁ to C ₂₀ alkyl group. _{Additionally ,} in _{Formula 1} , It may be a naphthyl group substituted with C ₁ to C ₁₀ alkyl or halogen, or a carbazolyl group unsubstituted or substituted with C ₁ to C ₁₀ alkyl or halogen, but is not limited thereto.

Meanwhile, Ar in Formula 1 may be an aromatic ring such as a benzene ring, naphthalene ring, anthracene ring, biphenyl ring, pyrene ring, or triphenylene ring. In one exemplary aspect, Ar may be a benzene ring, and the fluorene-based organic compound may have the structure of Formula 2 below.

[Formula 2]

In Formula 2, R ¹ to R ³ , Z and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

For example, the functional group containing Z in Formula 2 may be connected to the meta or para position with respect to the ether bond position of the benzene ring. In an exemplary aspect, the functional group containing Z may be connected in the para position with respect to the ether bond position of the benzene ring. For example, a fluorene-based organic compound in which Z in Formula 1 or Formula 2 may be ^* =X may have the structure of Formula 3 below.

[Formula 3]

In Formula 3, R ¹ to R ³ , X and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

Optionally, the fluorene-based organic compound in which Z may be ^* -Y in Formula 1 or Formula 2 may have the structure of Formula 4 below.

[Formula 4]

In Formula 4, R ¹ to R ³ , Y and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.

As will be described later, the composition for forming an organic film containing a fluorene-based organic compound having the structure of Formula 1 to Formula 4 has excellent heat resistance, gap-fill properties, and high planarization properties. Therefore, fluorene-based organic compounds having the structures of Formulas 1 to 4 can be used as a component for an organic layer for implementing a semiconductor micropattern, for example, a resist underlayer or a hard mask.

As long as the cured product of the fluorene-based organic compound having the structures of Formulas 1 to 4 can form a coating film on one side of the substrate, the molecular weight of the fluorene-based organic compound is not particularly limited. In one exemplary aspect, the molecular weight, for example, the weight average molecule (M _w ), of the fluorene-based organic compound having the structure of Formula 1 to Formula 4 may be 1,000 to 3,000, for example, 1,500 to 2,500.

When the molecular weight of the fluorene-based organic compound having the structure of Formula 1 to Formula 4 satisfies the above-mentioned range, sufficient thermal stability can be secured and excellent gap filling and planarization characteristics can be realized. Additionally, it can be stably dispersed in an organic solvent that may be included in the composition for forming an organic film. In one exemplary aspect, the weight average molecular weight (M _w ) of the fluorene-based organic compound having the repeating units of Formulas 1 to 4 is determined by gel-permeation chromatography (GPC) using polystyrene as a standard material. It can be measured using , but the present invention is not limited thereto.

Next, a method for producing a fluorene-based organic compound according to the present invention will be described. Among the fluorene-based organic compounds having the structures of Formulas 1 to 4, the terminal substituent is ketone or thio-ketone, that is, in Formula 1, Z is =X ¹ (X ¹ is O or S) Phosphorus fluorene-based organic compounds consist of a starting material in which six hydroxy groups are substituted in an aromatic ring substituted with fluorene, and an aromatic ring compound substituted with a halogen group such as a fluorine group and a ketone/thioketone group in the presence of a base. It can be prepared by performing a substitution reaction by reacting under the following conditions, optionally precipitating the product obtained by the reaction with a purification solvent, and separating the product and the solution. For example, a fluorene-based organic compound in which Z in Formula 1 is =X ¹ (X ¹ is O or S) can be synthesized according to synthesis scheme 1 below.

[Synthesis Scheme 1]

In Synthesis Scheme 1, R ¹ to R ³ , Ar, p, and q are each as defined in Formula 1, and X ¹ is O or S.

There is no limitation to the base that can be used in the above synthesis step, and in one exemplary aspect, the base that can be used in the process of synthesizing the fluorene-based organic compound according to synthesis scheme 1 includes sodium carbonate, potassium carbonate, etc., It is not limited. For 1 equivalent of the fluorene-based starting material having 6 hydroxy groups, the input amount of base may be 6 to 7 equivalents, for example, 6.1 to 6.2 equivalents.

If the amount of base used exceeds 7 equivalents per 1 equivalent of the fluorene-based starting material having 6 hydroxy groups, the amount of unreacted base increases and an excess amount of acid is required in the subsequent purification process. If the amount of base used is less than 6 equivalents per 1 equivalent of the fluorene-based starting material having 6 hydroxy groups, the synthetic reaction may not sufficiently occur, making it difficult to synthesize a fluorene-based organic compound with the desired structure.

In another optional aspect, the fluorene-based organic compound whose terminal functional group is a ketone or thioketone group according to Synthesis Scheme 1 is a fluorene-based organic compound where Z constituting the terminal functional group is =X ² (X ² is NR ⁴ ) It can be obtained by substituting the terminal functional group X ¹ of the fluorene-based organic compound obtained according to Synthesis Scheme 1 with X ² . As a ^{method of} substituting X ¹ with ^another At this time, if the reaction does not proceed, a Lewis acid or base catalyst containing an acid or metal may be used. At this time, it can be prepared by selectively precipitating the product obtained by the reaction with a purification solvent and separating the product and the solution.

[Synthesis Scheme 2]

In synthesis scheme 2, R ¹ to R ³ , Ar, p, and q are each the same as defined in Formula 1, and X ² is NR ⁴ .

The X ² reagent that can be used in the above synthesis step is not particularly limited. In ^one exemplary _{aspect , the} It is not limited to this. The amount of reagent added is 2 to 8 equivalents, preferably 6.1 to 6.5 equivalents, based on 1 equivalent of the fluorene-based organic compound finally synthesized in Synthesis Scheme 2. When ^the equivalent weight ^{of the} This can be achieved.

On the _other hand, if the amount of the A neutralizing agent is required. If the amount of _reagent

Optionally, an acid and/or a base may be used in the synthesis reaction according to Synthesis Scheme 2. Acids and bases that can be used in the synthesis step according to Synthesis Scheme 2 are not particularly limited. In one exemplary aspect, the acid that can be used in the synthesis reaction according to Synthesis Scheme 2 may be selected from the group consisting of paratoluenesulfonic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, and combinations thereof, but is not limited thereto. The base that can be used in the synthesis reaction according to Synthesis Scheme 2 may be selected from the group consisting of sodium bicarbonate, pyridine, sodium carbonate, potassium carbonate, and combinations thereof, but is not limited thereto.

In the synthesis reaction according to Synthesis Scheme 2, the input amount of acid or base is 0.1 to 3 equivalents, preferably 0.1 to 0.5 equivalents, based on 1 equivalent of the fluorene-based organic compound synthesized in Synthesis Scheme 2.

If the amount of acid or base used exceeds the above-mentioned range for 1 equivalent of the fluorene-based organic compound synthesized in Synthesis Scheme 2, the amount of unreacted acid or unreacted base increases, resulting in an excessive amount of neutralizing agent in the subsequent purification process. becomes necessary. If the amount of acid or base used is less than the above-mentioned range for 1 equivalent of the fluorene-based organic compound synthesized in Synthesis Scheme 2, the reaction may not occur sufficiently, and it may be difficult to obtain a compound with the desired structure.

Meanwhile, a fluorene-based organic compound in which the terminal functional group Z in Formula 1 has a single bond of -Y can be obtained by reducing the fluorene-based organic compounds obtained in the above-described synthesis schemes 1 and 2. That is, according to Synthesis Scheme 1 and Synthesis Scheme 2, a reduction reaction was performed by adding a reducing agent to a fluorene-based organic compound with Z = Afterwards, the product obtained by the reaction can optionally be precipitated with a purification solvent, and the product and the solution can be separated.

[Synthesis Scheme 3]

In Synthesis Scheme 3, R ¹ to R ³ , Ar, p, q, X, and Y are each the same as defined in Formula 1.

The reducing agent that can be used in the reduction step is not particularly limited. In one exemplary aspect, reducing agents include, but are not limited to, lithium-aluminum-hydride (LiAlH ₄ ), sodium-boro-hydride (NaBH ₄ ).

The amount of reducing agent added is 0.5 to 6 equivalents, preferably 2 to 4 equivalents, based on 1 equivalent of the fluorene-based organic compound obtained according to Synthesis Scheme 3. If the amount of reducing agent used exceeds the above-mentioned range for 1 equivalent of the finally synthesized fluorene-based organic compound, the amount of unreacted acid or unreacted base increases, and a large amount of hydrogen gas appears during the subsequent purification process, resulting in excessive A neutralizer is needed. If the amount of the reducing agent used is less than the above-mentioned range relative to 1 equivalent of the finally synthesized fluorene-based organic compound, the reaction does not occur sufficiently and a compound with the desired structure cannot be obtained.

When synthesizing fluorene-based organic compounds according to Synthesis Scheme 1 to Synthesis Scheme 3, reactants such as aromatic compounds having a hydroxy group, which are each starting material, are added to the synthesis solvent. At this time, the synthetic solvent that can be used in Synthesis Scheme 1 to Synthesis Scheme 3, respectively, can be any organic solvent that can mediate the synthesis reaction of the fluorene-based organic compound. Generally, the synthesis step is carried out in the presence of a soluble solvent capable of forming a homogeneous solution. For example, organic solvents include C ₂ -C ₁₀ aliphatic ethers, C ₂ -C ₁₀ aliphatic ketones, C ₃ -C ₁₀ aliphatic esters, C ₄ -C ₁₀ cycloaliphatic ethers, C ₄ -C ₁₀ cycloaliphatic ketones, C ₄ -C ₁₀ Cycloaliphatic ester, C ₁ -C ₁₀ aliphatic alcohol, unsubstituted or substituted C ₅ -C ₁₀ aromatic alcohol, C ₁ -C5 alkyl Substituted C ₃ -C ₁₀ aliphatic amide, C ₃ -C ₁₀ alkane , unsubstituted or C ₁ -C ₅ alkyl substituted C ₅ -C ₂₀ aryl, and combinations thereof.

More specifically, the synthetic solvent that can be used to synthesize a fluorene-based organic compound having Z as a terminal functional group from a fluorene-based starting material or a reactant that can be a fluorene-based organic compound is N-methyl-2-pyrrolidone. (N-methyl-2-pyrrolidone, NMP), dimethylformamide (N,N-Dimethylformamide, DMF), dimethylacetamide (N,N- Dimethylacetamide, DMAc), dimethyl sulfoxide (DMSO), dichlorobenzene It may be selected from the group consisting of (Dichlorobenzene), Mesitylene, Benzyl alcohol, Amyl alcohol, and combinations thereof, but the synthetic solvent usable in the present invention is not limited to these. .

In the synthesis reaction, as a reactant that can be used to synthesize fluorene-based organic compounds synthesized according to Synthesis Scheme 1 to Synthesis Scheme 3, the solid content of the aromatic compound or fluorene-based organic compound is such that the compound is uniformly distributed in the synthesis solvent. There is no particular limitation as long as it can be dissolved. The base used at this time is a catalyst, and in an undissolved state, only a local portion is instantaneously dissolved and can be removed through a simple removal process after the reaction has progressed, so it should be excluded from the solid content.

In one exemplary aspect, the amount of synthesis solvent used in each synthesis reaction according to Synthesis Scheme 1 to Synthesis Scheme 3 is about 5 to 60 parts by weight, preferably about 20 to 20 parts by weight, based on the total content of each reactant in the synthesis solvent. It can be adjusted to a range of 50 parts by weight. For example, the solid content of the reactant, which may be an aromatic compound having the hydroxy group or a fluorene-based organic compound whose terminal functional group may have a double bond such as a ketone/thioketone, is 20 to 50 parts by weight, preferably 25 to 25 parts by weight. 45 parts by weight, the synthetic solvent can be used in a ratio of 50 to 80 parts by weight, preferably 55 to 75 parts by weight. Unless otherwise stated herein, 'parts by weight' is interpreted to mean the relative weight ratio between the different ingredients being combined.

Meanwhile, after the synthesis reaction of the fluorene-based organic compound according to Synthesis Scheme 1 to Synthesis Scheme 3 is completed, a step for removing unreacted raw materials, catalysts, etc. present in the reaction system may be performed. For example, a method of removing volatile components by raising the temperature of the reaction tank cooled to room temperature after completion of the synthesis reaction to 130 ~ 230°C, a method of adding an appropriate solvent and then filtering and separating the undissolved solid material, and A method of dissolving the synthesized fluorene-based organic compound in a positive solvent and then re-precipitating it in an anti-solvent may be used.

For example, a purification solvent may be used to separate the fluorene-based organic compound, which is a product obtained from a synthesis reaction, from the solution used in the synthesis process. The purification solvent is used to precipitate the product obtained by the synthesis reaction and separate the solution from the precipitated product. In one exemplary embodiment, the purification solvent may be a C ₃ -C ₁₀ alkane such as hexane, a C ₁ -C ₅ alcohol such as methanol, ethanol, and/or water (such as distilled water), although the purification solvent may be any of these. It is not limited.

[Composition for forming organic films, organic films, pattern formation methods and applications]

According to another aspect, the present invention provides a composition for forming an organic film containing a fluorene-based organic compound having the structure of Formula 1 to Formula 4, an organic film obtainable from the composition for forming an organic film, and manufacturing an organic film using the same. It relates to a method and a method of forming a resist pattern.

The composition for forming an organic film includes a fluorene-based organic compound having the structure of Formula 1 to Formula 4, a polymer for film thickness enhancement if necessary, and an organic solvent for dispersing the fluorene-based organic compound and the polymer for film thickness enhancement. It can be included. An organic film can be manufactured by curing the composition for forming an organic film, and a desired pattern can be formed as needed.

An organic film having excellent heat resistance, gap fill properties, and planarization properties can be manufactured using a composition for forming an organic film containing a fluorene-based organic compound having the structure of Formula 1 to Formula 4. In one exemplary aspect, the organic film containing the cured product of the fluorene-based organic compound having the structure of Chemical Formula 1 to Chemical Formula 4 is an organic film that requires a high temperature process for a photoresist underlayer or hard mask in a photolithography process. It can be used as a membrane, etc.

For example, in the composition for forming an organic film, the fluorene-based organic compound having the structure of Formula 1 to Formula 4 is added at a ratio of 2.5 to 30 parts by weight, for example, 2.5 to 25 parts by weight, and the organic solvent is added at a ratio of 70 to 97.5 parts by weight. It may be added at a ratio of 75 to 97.5 parts by weight, for example. Accordingly, when the composition for forming an organic film is applied to a substrate such as a substrate, workability and safety of the composition for forming an organic film can be improved.

If the content of the fluorene-based organic compound having the structure of Chemical Formula 1 to Chemical Formula 4 in the composition for forming an organic film exceeds the above-mentioned range, and the content of the organic solvent is less than the above-mentioned range, the concentration of the composition for forming an organic film is excessive. As the temperature rises, the coating process may become difficult. On the other hand, if the content of the fluorene-based organic compound having the structure of Formula 1 to Formula 4 in the composition for forming an organic film is less than the above-mentioned range, and the content of the organic solvent exceeds the above-mentioned range, it is difficult to obtain an organic film with the desired characteristics. Coating properties may actually deteriorate.

Organic solvents that can be added to the composition for forming an organic film include C ₂ -C ₁₀ aliphatic ether, C ₂ -C ₁₀ aliphatic ketone, C ₃ -C ₁₀ aliphatic ester, C ₄ -C ₁₀ alicyclic ether, C ₄ -C ₁₀ cycloaliphatic ketone, C ₄ -C ₁₀ cycloaliphatic ester, C ₁ -C ₁₀ aliphatic alcohol, unsubstituted or substituted C ₅ -C ₁₀ aromatic alcohol, C ₁ -C ₅ alkyl substituted C ₃ -C ₁₀ aliphatic amide , C ₃ -C ₁₀ alkane, unsubstituted or C ₃ -C ₁₀ alkyl substituted C ₅ -C ₂₀ aryl, and combinations thereof.

Specifically, the organic solvent that can be added to the composition for forming an organic film is propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol dimethyl ether. Acetate (Propylene glycol diacetate, PGDA), Propylene glycol normal propyl ether (PnP), Propylene glycol normal butyl ether (PnB), butyl cellosolve (BC), Methyl cellosolve (MC), ethylene glycol (EG), Propylene glycol (PG), Cyclohexanone, γ-butyrolactone (GBL), ethyl Ethyl lactate, n-butylacetate (NBA), N-methyl-2-pyrrolidone (NMP), dimethylformamide (N,N-Dimethylformamide, DMF), dimethyl acetamide (N,N-Dimethyl acetamide, DMAc), tetra-hydrofuran (THF), ethyl-3-ethoxypropionate, toluene, Xylene, Butylacetate, Acetone, Methyl ethyl ketone, Methyl isobutylketone, Methanol, Ethanol, n-propanol (n) -propanol, isopropanol (IPA), butanol, butoxy ethanol, pentanol, octanol, hexane (n-Hexane), heptane, ether ( It may be selected from the group consisting of ether, ketone, and combinations thereof, but the present invention is not limited thereto.

When the composition for forming an organic film according to the present invention is used to form, for example, a resist underlayer film or an organic film, the composition for forming an organic film may be combined with a polymer for film thickness enhancement and added as necessary. When such a film thickness enhancing polymer is included in the composition for forming an organic film, a strong organic film can be formed on one side of the substrate.

The polymer for increasing film thickness may be a polymer having an aromatic alcohol structure. In an exemplary aspect, the polymer for enhancing film thickness may include a fluorene-based polymer containing phenol or naphthol (naphthalene-alcohol) and/or a bisphenol-based polymer. For example, the weight average molecular weight (M _w ) of the polymer for increasing the harness thickness may be 2000 to 40000, for example, 5000 to 30000, but is not limited thereto.

If the weight average molecular weight (M _w ) of the film thickness enhancing polymer used as an additive in the organic film forming composition exceeds the above-mentioned range, when applying the organic film forming composition containing the film thickness enhancing polymer, Gap-fill may not be sufficiently achieved, and the solubility in the solvent may be lowered, which may cause problems with the storage stability of the composition. In one exemplary aspect, the weight average molecular weight (M _w ) of the film thickness enhancing polymer may be measured using gel-permeation chromatography (GPC) using polystyrene as a standard material, but this The invention is not limited to this.

In an illustrative aspect, the polymer for increasing film thickness may include at least one of a fluorene-based polymer having a repeating unit of Formula 5 below and a bisphenol-based polymer having a repeating unit of Formula 6 below.

[Formula 5]

[Formula 6]

In Formulas 5 and 6, A and B are each independently a C ₆ to C ₃₀ aromatic ring or a C ₃ to C ₃₀ heteroaromatic ring; R ¹¹ is each independently hydrogen, a glycidyl group, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, a C ₄ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ heteroaryl group. appointment; R ¹² and R ¹³ are each independently hydrogen, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, a C ₄ to C ₂₀ cycloalkyl group, a C ₆ to C ₂₀ aryl group, or a C ₃ to C ₂₀ heteroaryl group. ; L ₁ and L ₂ are each independently a single bond, an ether group, an ester group, a C ₁ to C ₁₀ alkylene group, a C ₆ to C ₂₀ arylene group, or a C ₃ to C ₂₀ hetero arylene group; m and n are each independently integers from 0 to 2, and when m and n are plural, each R ¹¹ and each R ¹² may be different or the same; q is the number of substituents other than hydrogen and is an integer from 0 to 4, and when q is plural, each R ¹³ may be different or the same.

For example, in Formula 5 and Formula 6, A and B may each independently be a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a biphenyl ring, a triphenylene ring, a pyrene ring, or a carbazole ring. It is not limited to this.

According to an exemplary aspect, when the solid content of the composition for forming an organic film includes a fluorene-based organic compound having the structure of Formula 1 to Formula 4, and a film thickness enhancement polymer that may have the structure of Formula 5 and Formula 6, The content of the fluorene-based organic compound in the total solid content may be at least 25 parts by weight, for example, 25 to 80 parts by weight.

For example, the content of the fluorene-based organic compound having the structure of Formula 1 to Formula 4 in the entire composition for forming an organic film including the organic solvent may be at least 2.5 parts by weight, for example, 2.5 to 30 parts by weight. If the content of the fluorene-based organic compound in the composition for forming an organic film is less than 2.5 parts by weight, the heat resistance characteristics, gap-fill characteristics, planarization characteristics, etc. of the finally manufactured organic film may not be sufficiently expressed.

In one exemplary aspect, the fluorene-based organic compound having the structure of Formula 1 to Formula 4 is added in a ratio of 2.5 to 30 parts by weight, preferably 2.5 to 15 parts by weight, in the composition for forming an organic film, to increase the film thickness. The polymer may be added at a rate of 0 to 30 parts by weight, preferably 0 to 27.5 parts by weight, and the organic solvent may be added at a rate of 40 to 97.5 parts by weight, preferably 70 to 95 parts by weight.

As a non-limiting example, the composition for forming an organic film to form a low thickness may include 3 to 10 parts by weight, for example, 4.9 parts by weight, of a fluorene-based organic compound having the structure of Formula 1 to Formula 4 and film thickness enhancement. It may be composed of 0.05 to 1.0 parts by weight, for example, 0.1 parts by weight of the polymer, and 90 to 99 parts by weight, for example, 95 parts by weight of the organic solvent. As another non-limiting example, the composition for forming an organic film to create a high thickness may include 7 to 15 parts by weight of a fluorene-based organic compound, for example, 10 parts by weight, and 15 to 25 parts by weight of a polymer for enhancing film thickness. , for example, 20 parts by weight, 65 to 75 parts by weight, for example, 70 parts by weight of an organic solvent.

If the content of the polymer for film thickness enhancement in the composition for forming an organic film exceeds the above-mentioned range, the polymer for film thickness enhancement is included in excess compared to the fluorene-based organic compound having the structure of Formula 1 to Formula 4, thereby reducing the desired heat resistance. And it may be difficult to obtain an organic film with flattening characteristics.

A composition for forming an organic film can be prepared by mixing a fluorene-based organic compound having the structure of Formula 1 to Formula 4, and optionally a film thickness enhancing polymer, with an appropriate organic solvent, and curing the composition for forming an organic film, An organic film containing a cured product of a fluorene-based organic compound can be manufactured, and if necessary, a pattern of a desired semiconductor device can be formed.

For example, a composition for forming an organic film containing a fluorene-based organic compound having the structure of Formula 1 to Formula 4 is coated on the top of the substrate, and then the organic solvent is removed by a method such as heat treatment to form the fluorene-based organic compound. An organic film containing the cured product can be formed. The method of coating the composition for forming an organic film on the top of the substrate is not particularly limited.

In addition, when the composition for forming an organic film according to the present invention is used to form, for example, a resist underlayer film or an organic film, the composition for forming an organic film may optionally contain at least one selected from a surfactant, an adhesion improver, and a crosslinking agent. Additional additives may be included. In addition, the composition for forming an organic film may further include other additives such as stabilizers, leveling agents, and anti-foaming agents. These functional additives may be added to the composition for forming an organic film in an amount of, for example, 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight.

The surfactant improves adhesion between the composition for forming an organic film according to the present invention and the substrate. 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 can be used in combination. Specific examples of surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl allyl ethers, polyoxyethylene polyoxypropylene block copolymers, and sorbitol. It may contain nonionic surfactants such as bitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyacrylates.

A cross-linking agent that may be included in the composition for forming an organic film as needed is for inducing a cross-linking reaction between fluorene-based organic compounds having the structures of Formulas 1 to 4 and may be a heat-crosslinking agent. . The crosslinking agent that can be added to the composition for forming an organic film is not particularly limited.

For example, cross-linking agents that can be added to the composition for forming an organic film include melamine-based cross-linking agents such as melamine formaldehydes, benzoguanine-based cross-linking agents such as benzoguanine-formaldehydes, and glycoluryl-based cross-linking agents such as glycoluryl formaldehydes. , one or more types may be selected from urea-based crosslinking agents such as urea formaldehyde, phenol-based crosslinking agents, benzyl alcohol crosslinking agents, epoxy-based crosslinking agents, isocyanate, and alkoxy methyl melamine-based crosslinking agents. Commercially available crosslinking agents are well known and readily available. In the composition for forming an organic film according to the present invention, the crosslinking agent may be added in an amount of 0 to 5 parts by weight, preferably 0 to 0.5 parts by weight. If the above-mentioned range is exceeded, the stability of the organic film may be reduced.

If necessary, the composition for forming an organic film may further include an acid generator as a crosslinking accelerator. The acid generator is used to activate the crosslinking reaction between the above-described crosslinking agent and the fluorene-based organic compounds having the structures of Formulas 1 to 4. After applying the composition for forming an organic film containing an acid generator to an appropriate substrate, performing a heat treatment process such as a baking process can promote the crosslinking reaction in the presence of the acid generated from the acid generator. An organic film that is insoluble in the resist solvent can be formed. The acid generator may be mixed in the composition for forming an organic anti-reflective film according to the present invention at a ratio of 0.01 to 4 parts by weight, preferably 0.01 to 0.4 parts by weight.

For example, the acid generator that can be added to the composition for forming an organic film is an onium salt-based acid generator that can be selected from diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, and combinations thereof, and sulfonyl salts. Diazomethane-based acid generator, N-sulfonyloxyimide-based acid generator, benzoin sulfonate-based acid generator, nitrobenzyl sulfonate-based acid generator, sulfone-based acid generator, glyoxime-based acid generator, One or more types may be selected from triazine-based acid generators, etc. For example, as the acid generator, at least one compound selected from aromatic sulfonic acid, alicyclic sulfonic acid, sulfosalicic acid, and salts thereof can be used. For example, one or more types may be selected from pyridinium-p-toluenesulfonic acid, 2,6-dimethylpyridinium-p-toluenesulfonic acid, 2,4,6-trimethylpyridinium-p-toluenesulfonic acid, etc.

The adhesion improver improves the adhesion between the inorganic material used as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, and the organic film formed according to the present invention. The type of adhesion improving agent is not particularly limited, and specific examples include silane-based coupling agents or thiol-based compounds, and preferably silane-based coupling agents.

As a stabilizer, a light stabilizer can be used to improve the light resistance of the organic film produced according to the present invention. The type of stabilizer is not particularly limited, and specific examples include one or two or more types of benzotriazole-based, triazine-based, benzophenone-based, hindered aminoether-based, and hindered amine-based compounds. Can be used together.

Using the composition for forming an organic film prepared according to the present invention, an organic film having excellent heat resistance, etching resistance, gap fill characteristics, and high planarization characteristics can be formed. Therefore, the composition for forming an organic film can be applied to an appropriate substrate and cured to be used as a resist underlayer or hard mask layer between the substrate and the resist layer in the photoresist process for implementing fine patterns of semiconductor devices or display devices.

Therefore, according to another aspect, the present invention includes a cured product by cross-linking of a fluorene-based organic compound having the structure of Formula 1 to Formula 4, for example, a cured product by cross-linking of the composition for forming an organic film described above. It relates to an organic film or resist underlayer film, a method of forming the organic film, a method of forming an appropriate resist pattern on top of a substrate, and a semiconductor device manufactured by this method.

In order to manufacture an organic film from the above-described composition for forming an organic film, an appropriate composition for forming an organic film containing a fluorene-based organic compound having the structure of Formula 1 to Formula 4, an organic solvent, and, if necessary, a polymer for enhancing film thickness is used. After being applied on a substrate, the composition for forming an organic film can be pre-baked at a predetermined temperature.

In an exemplary embodiment, the composition for forming an organic film described above is coated on a suitable substrate. The substrate on which the composition for forming an organic film is coated is not particularly limited. For example, the composition for forming an organic film may be coated on a glass substrate, a transparent plastic substrate, a silicon wafer, or a SiO ₂ wafer.

Methods for coating the composition for forming an organic film according to the present invention on a suitable substrate include spin coating such as the central drop spin method, roll coating, spray coating, bar coating, and slit coating using a slit nozzle such as discharge nozzle coating. Methods can be used, and coating can be done by combining two or more coating methods. At this time, the thickness of the coated film may vary depending on the coating method, the concentration of solids in the composition for forming an antireflection film, viscosity, etc., but for example, it may be applied at a thickness of 50 to 2000 nm.

Next, a heat treatment (baking) process, for example, a pre-heat treatment process, may be performed on the composition for forming an anti-reflection film coated on the substrate. Through this process, the solvent of the composition for forming an organic film coated on the substrate is volatilized to obtain a coating film. In this process, the organic solvent is typically volatilized by applying appropriate heat, for example, in the case of hot plate heating, 60 to 550°C, preferably 100 to 350°C, more preferably 100 to 250°C. It may be performed for 10 to 300 seconds, and if a heat oven is used, it may be performed at 60 to 550°C, preferably 100 to 350°C, more preferably 100 to 250°C for 20 to 500 seconds, but is limited thereto. It doesn't work.

Meanwhile, the composition for forming an organic film described above can be used in a process of forming a resist pattern such as a semiconductor micropattern. For example, a method of forming a resist pattern includes the steps of applying the above-described composition for forming an organic film on top of a substrate (e.g., a silicon wafer substrate on which a metal layer such as an aluminum layer is formed), and the organic film forming composition applied on the substrate. Curing the composition for forming a film to form an organic film as a lower layer on a substrate, optionally forming an intermediate layer on top of the organic film, and forming a resist film by applying a photoresist on the organic film or the middle layer. It may include performing an exposure process to form a resist pattern by exposing the formed resist film to a light source in a predetermined pattern, and performing a development process on the exposed resist film to finally form a resist pattern. . If necessary, after forming a resist pattern, etching the lower layer film using the resist pattern as a mask to obtain a patterned lower layer film, and etching the substrate using the patterned lower layer film as a mask to form a pattern on the substrate. The step of forming may be further included.

Optionally, when an intermediate layer film is formed between the lower layer film and the resist film, etching the middle layer film using the resist pattern as a mask to obtain a patterned middle layer film, and etching the lower layer film using the patterned middle layer film as a mask to form a patterned lower layer. It may further include obtaining a film and etching the substrate using the patterned lower layer as a mask to form a pattern on the substrate.

For example, the intermediate layer film is titanium nitride (TiO _x ), titanium oxynitride (TiO _x N _y ), silicon oxide ( _{SiO x )} , silicon oxynitride ( _SiO and a combination thereof, but is not limited thereto. For example, the middle layer film can be formed on the lower layer film using chemical vapor deposition (CVD) at high temperature, and can be made of, for example, a silicon oxynitride material with excellent anti-reflection effect. The thickness of the intermediate layer is 5 to 200 nm, for example 10 to 100 nm. For example, when forming an intermediate layer film, the deposition temperature may be 240 to 500°C.

Since the fluorene-based organic compounds having the structures of Formulas 1 to 4 have high thermal stability, even if an intermediate layer film made of an inorganic material is formed, the resist underlayer film containing the cured product of the fluorene-based organic compound is not thermally decomposed. No. In other words, it is possible to prevent the inside of the equipment from being contaminated by decomposition of the resist lower layer film during the middle layer film forming process performed at high temperature.

If necessary, a heat treatment (baking) process, for example, a post-baking process, may be additionally performed before and after the exposure process.

Specifically, the following process may be performed to form a predetermined pattern on the top of the substrate. The composition for forming an organic film described above is applied on the top of the substrate, a pre-heat treatment process is performed to form an organic film, and a photoresist is applied on top of the organic film to form a predetermined resist film. In an optional aspect, an intermediate layer film made of an inorganic material may be formed on the organic film and the resist film.

Next, the photoresist can be selectively exposed according to a predetermined pattern to form a resist film with a pattern. Exemplarily, the exposure process may be performed using an excimer laser (e.g., ArF excimer laser with a wavelength of 193 nm, KrF excimer laser, EUV, deep ultraviolet ray, ultraviolet ray, visible light, electron beam, X-ray or g-ray (wavelength 436 nm), h- It can be performed by irradiating light (wavelength 405 nm), i-ray (wavelength 365 nm), or a mixture of these.

In order for this exposure process to be performed smoothly, exposure equipment such as a mask aligner, stepper, and scatterer can be used on the resist film located on top of the organic film for which the pre-baking process has been completed. Exposure may be performed using contact, proximity, or projection exposure methods. Exposure energy may vary depending on the sensitivity of the produced resist film, but usually an exposure energy of 30 to 300 mJ/cm ² , preferably 30 to 200 mJ/cm ² can be applied.

After the exposure process is completed, in order to obtain a final patterned resist film, the substrate with the organic film applied and the resist film are dipped in an appropriate developer solution or the developer solution is sprayed on the substrate to remove the film in the exposed area, or CHF ₃ /CF ₄ It can be performed through dry etching using mixed gas, etc. The developing solution is an alkaline inorganic alkali compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, or potassium silicate, or an organic alkaline aqueous solution such as triethylamine, triethanolamine, tetramethylammonium hydroxide, or tetraethylammonium hydroxide. can be used. For example, a 0.01 to 5% (w/v) aqueous solution of tetramethylammonium hydroxide can be used as a developer.

Additionally, in an optional aspect, a plasma etching process using Cl ₂ or HBr gas may be performed to etch the substrate exposed in a predetermined pattern by removing the organic layer.

The resist underlayer film of an organic material containing a cured product of a fluorene-based organic compound prepared according to the method of the present invention described above has excellent gap filling and planarization properties and good thermal stability. Therefore, it can be usefully used as an underlayer between the substrate and the resist film in photoresist processes using EUV wavelengths as well as KrF (248 nm) and ArF (193 nm) wavelengths.

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

Synthesis Example 1: Synthesis of fluorene-based organic compounds

[Scheme 1]

5,5'-(9H-fluorene-9,9'-diyl)bis(benzene-1,2) in a reaction vessel containing N-methyl-2-pyrrolidone (NMP) (40.27 g) under nitrogen atmosphere. ,3triol) (6.22 g, 15 mmol) and 4-fluoropropiophenone (13.92 g, 90.15 mmol) were added and dissolved at 50°C, then potassium carbonate (12.65 g, 90.15 mmol) was added as a catalyst, The mixture was refluxed and stirred at 170°C for 8 hours. After the stirring was completed, the solution was filtered and passed through 50 mL of ion exchange resin (Trilite, SCR-BH, Samyang Corporation) washed with N-methyl-2-pyrrolidone (NMP), followed by 10 times the volume of the reaction solution. Methanol was poured to precipitate. The precipitate was dried under vacuum at 60°C for 72 hours to synthesize a fluorene-based organic compound containing a ketone group as a terminal functional group. Next, the weight average molecular weight of the fluorene-based organic compound was measured using gel permeation chromatography (GPC). GPC column (Styragel HR 1, Styragel HR 3: Water, 7.8 mm The measurement conditions were column temperature of 4°C, measurement concentration of 10%, injection volume of 20 μL, carrier solvent tetrahydrofuran (THF), flow rate of 1 mL/min, standard sample calibration curve, and standard polystyrene (Shodex, model name: SL-105). As a result of GPC analysis of the obtained single compound, the weight average molecular weight (M _w ) was about 1,200.

Synthesis Example 2: Synthesis of fluorene-based organic compounds

[Scheme 2]

Dean-Stark solution containing tetrahydrofuran (THF, 85.1 g), distilled water (H ₂ O, 9.9 g), sodium hydroxide (NaOH, 4.96 g, 0.124 mol) and toluene (33.5 g) under a nitrogen atmosphere. (((5-(9-(3-(3-(4-methoxybenzoyl)phenoxy)phenyl)-9H-fluoren-9-yl)benzene-1, Add 2,3-tril)tris(benzene-4,1-diyl)tris(4-methoxyphenyl)methanone (33.52 g, 0.02 mol) and hydroxyamine hydrochloride (9.03 g, 0.13 mmol) and mix from 25 to 6. Over time, the temperature was gradually raised to 100° C. and stirred for 6 hours. Afterwards, the temperature was raised to 120° C. and stirred for an additional 2 hours. After the stirring was completed, the solution was cooled, and distilled water 10 times the amount of the reaction solution was poured into the solution to cause precipitation. The precipitate was dried under vacuum at 50°C for 12 hours to synthesize a fluorene-based organic compound containing =NOH as a terminal functional group. As a result of GPC analysis, the weight average molecular weight (M _w ) was measured to be approximately 1,800.

Synthesis Example 3: Synthesis of fluorene-based organic compounds

[Scheme 3]

(((5-(9-(3-(4-(4-(4-phenol)) in a reaction vessel containing propylene glycol methyl ester (PGME, 82 g) and tetrahydrofuran (THF, 123 g) under a nitrogen atmosphere. si)benzoyl)phenoxy)-4,5-bis(4-(4-phenoxybenzoyl)phenoxy)phenyl)-9H-fluoren-9-yl)benzene-1,2,3-tril)tris( Add oxy)tris(benzene-4,1-dyl))tris((4-phenoxyphenyl)methanone) (40.96 g, 20 mmol) and sodium borohydride (NaBH ₄ , 4.54 g, 120 mmol). After dissolution at 50°C, it was refluxed and stirred for 6 hours at 60°C. After cooling the solution to 10°C, a mixture of acetic acid (10 g) and propylene glycol methyl ester (PGME, 20 g) was slowly added. It was added dropwise. After the generation of bubbles stopped, 20 times more water than the reaction solution was poured to precipitate. The precipitate was filtered, washed with a mixture of methanol and water, and dried in a vacuum at 40°C for 72 hours to synthesize the following compound. Next, the weight average molecular weight of the compound was measured using gel permeation chromatography (GPC). GPC column (Styragel HR 1, Styragel HR 3: Water, 7.8 mm Measurement concentration 10%, injection volume 20 μL, carrier solvent tetrahydrofuran (THF), flow rate 1 mL/min, standard sample calibration curve standard polystyrene (Shodex, model name: SL-105) was used. GPC analysis results for the single compound obtained. , the weight average molecular weight (Mw) was about 2,350.

Preparation Example 1: Synthesis of fluorene-based polymer

[Fluorene-based polymer]

4,4'-(9H-fluorene-9,9-dyl)diphenol (106.142 g, 0.300 mol) and paraform were added to a reaction vessel containing propylene glycol monomethyl ether acetate (PGMEA, 345 g) under a nitrogen atmosphere. Aldehyde (8.918 g, 0.294 mol) and paratoluenesulfonic acid (0.576 g, 0.003 mmol) as a catalyst were added, stirred to dissolve, and stirred for 12 hours at 100°C under reflux atmosphere. After the stirring was completed, the solution was cooled to room temperature, then 5 times the amount of methanol as the reaction solution was poured, and 5 times the amount of distilled water was poured into it to precipitate it. The precipitate was dried in vacuum at 60°C for 24 hours to obtain a fluorene-based polymer. As a result of GPC analysis, the weight average molecular weight (M _w ) of the following fluorene-based polymer according to the standard polystyrene conversion method was measured to be about 18,000.

Preparation Example 2: Bisphenol-based polymer synthesis

[Bisphenol-based polymer]

In a reaction vessel containing propylene glycol monomethyl ether acetate (PGMEA, 234 g) under a nitrogen atmosphere, bisphenol A (69.18 g, 0.300 mol), paraformaldehyde (8.918 g, 0.294 mol), and paratoluenesulfonic acid (0.576 g) were added as a catalyst. , 0.003 mmol) was added, stirred to dissolve, and then stirred for 12 hours at 80°C under reflux atmosphere. After the stirring was completed, the solution was cooled to room temperature, and then 5 times the amount of methanol as the reaction solution was poured, followed by 5 times the amount of distilled water to precipitate it. The precipitate was dried in vacuum at 60°C for 24 hours to obtain a bisphenol-based polymer. As a result of GPC analysis, the weight average molecular weight (M _w ) of the bisphenol-based polymer according to the standard polystyrene conversion method was measured to be about 21,800.

Example 1: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 1 was dissolved in a mixed solution of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone and then filtered to prepare a composition for forming an organic film.

Example 2: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 2 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and then filtered to prepare a composition for forming an organic film.

Example 3: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 3 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and then filtered to prepare a composition for forming an organic film.

Example 4: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 2 and the fluorene-based polymer obtained in Preparation Example 1 were mixed in a weight ratio of 5:5, and the mixture was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and then filtered to obtain organic A composition for film formation was prepared.

Example 5: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 3 and the fluorene-based polymer obtained in Preparation Example 1 were composed in a weight ratio of 5:5, and this mixture was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and filtered to form an organic membrane. A composition for forming was prepared.

Example 6: Preparation of composition for forming organic film

The fluorene-based organic compound obtained in Synthesis Example 3 and the bisphenol-based polymer obtained in Preparation Example 2 were mixed in a weight ratio of 7:3, and this mixture was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and filtered to form an organic film. A composition was prepared.

Comparative Example 1: Preparation of composition for forming organic film

The fluorene-based polymer obtained in Preparation Example 1 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and then filtered to prepare a composition for forming an organic film.

Comparative Example 2: Preparation of composition for forming organic film

The bisphenol-based polymer obtained in Preparation Example 2 was dissolved in propylene glycol monomethyl ether acetate (PGMEA) and then filtered to prepare a composition for forming an organic film.

Experimental Example 1: Organic film production and heat resistance evaluation

The compositions for forming organic films according to Examples 1 to 6 and Comparative Examples 1 to 2 were spin-coated to a thickness of 5000 Å on a silicon wafer, and then cured by baking at 400°C for 1 minute. Next, a sample was collected by scraping the film on the top of the wafer, and the weight remaining after sublimation to 400°C was measured at a temperature increase rate of 10°C per second through thermogravimetric analysis (TGA) in nitrogen gas. The remaining weight portion upon reaching 400°C is shown in Table 1 below. Figures 1 to 3 show the results of thermogravimetric analysis of organic films obtained from the compositions for forming organic films prepared according to Examples 3, 5, and Comparative Example 1, respectively. As shown in Table 1 and Figures 1 to 3, the organic film containing the fluorene-based organic compound synthesized in Synthesis Examples 1 to 3 confirmed that most of the organic film components remained without being thermally decomposed even at high temperatures. did.

Thermogravimetric analysis of the ratio of ingredients remaining when reaching 400℃ compared to the initial ingredients Sample Thermogravimetric analysis (%) (400℃) Example 1 97.1 Example 2 96.3 Example 3 97.8 Example 4 94.4 Example 5 97.0 Example 6 93.2 Comparative Example 1 89.2 Comparative Example 2 83.2

Experimental Example 2: Evaluation of flattening characteristics

The hardmask composition according to Examples 1 to Comparative Examples 1 was applied on a silicon wafer with a pattern of 1000 Å in height. After spin coating and curing at 400°C for 1 minute, the flattening characteristics were observed using a field emission scanning electron microscope (FE-SEM) equipment. The flattening characteristics were quantified using the following calculation equation 1. h ₂ and h ₃ are designated by specifying one of the patterns 1.8 to 2.2 ㎛ left of h ₁ . The flattening characteristics are better the closer the average value of h ₂ and h ₃ is to the value of h ₁ , and the smaller the flatness value, the better the performance.

[Smoothing Calculation]

Flatness = h ₁ - {(h ₂ +h ₃ )/2}

The results of measuring the degree of flatness of the organic films prepared according to Examples and Comparative Examples are shown in Table 2 below. In addition, SEM images of the cross-sectional profiles of organic films prepared from the compositions for forming organic films prepared in Example 3, Example 5, and Comparative Example 2 are shown in Figures 4 to 6, respectively. As shown in Table 2 and FIGS. 4 to 6, it was confirmed that the organic film containing the fluorene-based organic compound synthesized in Synthesis Examples 1 to 3 could achieve excellent planarization characteristics.

Measuring the flatness of organic films Sample Flatness Example 1 145 Example 2 99 Example 3 84 Example 4 124 Example 5 81 Example 6 86 Comparative Example 1 452 Comparative Example 2 298

Experimental Example 3: Evaluation of organic film thickness implementation

The compositions for forming organic films according to Examples 4 to 6 and Comparative Examples 1 to 2 were spin-coated to a thickness of 20,000 Å on a silicon wafer, and then cured by baking at 400°C for 1 minute. After measuring the thickness at 25 points within the wafer through ellipsometer analysis, the thickness realization of the organic film was evaluated according to ((maximum value) - (minimum value))/(average value x 2). The evaluation results are shown in Table 3 below. In Table 3, coating defects mean that a coating film is formed over an area of more than 90% of the silicon wafer and the thickness exceeds 20,000 Å, but there are a significant number of microbubbles on a microscope and the thickness difference between positions of the formed coating film is significant. As shown in Table 3, it was confirmed that an organic film of the desired thickness could be formed even in the organic film containing the fluorene-based organic compound synthesized in the synthesis example.

Evaluation of the thickness of the organic layer Sample Thickness implementation and ellipsometer analysis Example 4 1.61% Example 5 0.74% Example 6 0.86% Comparative Example 1 poor coating Comparative Example 2 poor coating

Although the present invention has been described above based on exemplary embodiments and examples of the present invention, the present invention is not limited to the technical ideas described in the above embodiments and examples. Rather, anyone skilled in the art to which the present invention pertains can easily make 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 rights of the present invention.

Claims (17)

A fluorene-based organic compound having the structure of Formula 1 below.
[Formula 1]

In Formula 1, R ¹ is hydrogen, a C ₁ to C ₂₀ alkyl group, or a C ₆ to C ₃₀ aryl group, and the C ₆ to C ₃₀ aryl group is a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, or C ₆ ~C ₃₀ may be further substituted with another functional group, which is an aryloxy group; R ² to R ³ are each independently hydrogen or a C ₁ to C ₂₀ alkyl group; Each R ¹ may be different or the same; p is the number of substituents other than hydrogen and is an integer of 0 to 10, q is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same, and q When there is a plurality, each R ³ may be different or the same; Each Z is independently ^* =X or ^* -Y (asterisks indicate linkages), and each Z may be different or the same; X is each independently NR ⁴ , O or S, and R ⁴ is hydrogen, a hydroxy group, a C ₁ to C ₂₀ alkyl group, or a C ₁ to C ₂₀ alkoxy group; Y is each independently a hydroxy group or a C ₁ to C ₂₀ alkoxy group; Ar is an aromatic ring that is a benzene ring, naphthalene ring, anthracene ring, pyrene ring, or triphenylene ring.
The fluorene-based organic compound according to claim 1, wherein the fluorene-based organic compound has the structure of Formula 2 below.
[Formula 2]

In Formula 2, R ¹ to R ³ , Z and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.
The fluorene-based organic compound according to claim 1, wherein the fluorene-based organic compound has the structure of Formula 3 below.
[Formula 3]

In Formula 3, R ¹ to R ³ , X and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.
The fluorene-based organic compound according to claim 1, wherein the fluorene-based organic compound has the structure of the following formula (4).
[Formula 4]

In Formula 4, R ¹ to R ³ , Y and q are as defined in Formula 1; p is the number of substituents other than hydrogen and is an integer of 0 to 4, and when p is plural, each R ² may be different or the same.
The fluorene-based organic compound according to claim 1, wherein p and q in Formula 1 are each independently an integer of 0 to 2.
The fluorene-based organic compound according to claim 1; and
A composition for forming an organic film comprising an organic solvent for dispersing the fluorene-based organic compound.
The method of claim 6, further comprising a film thickness enhancing polymer, wherein the film thickness enhancing polymer is at least one of a fluorene-based polymer having a repeating unit of the following formula (5) and a bisphenol-based polymer having a repeating unit of the following formula (6) A composition for forming an organic film comprising a.
[Formula 5]

[Formula 6]

In Formulas 5 and 6, A and B are each independently a C ₆ to C ₃₀ aromatic ring; R ¹¹ is each independently hydrogen or a C ₁ to C ₁₀ alkyl group; R ¹² and R ¹³ are each independently hydrogen or a C ₁ to C ₁₀ alkyl group; L ₁ and L ₂ are each independently a single bond or a C ₁ to C ₁₀ alkylene group; m and n are each independently integers from 0 to 2, and when m and n are plural, each R ¹¹ and each R ¹² may be different or the same; q is the number of substituents other than hydrogen and is an integer from 0 to 4, and when q is plural, each R ¹³ may be different or the same.
The composition for forming an organic film according to claim 7, wherein the weight average molecular weight (M _w ) of the film thickness enhancing polymer is 2000 to 4000.
The composition for forming an organic film according to claim 7, wherein the content of the fluorene-based organic compound is at least 25 parts by weight based on 100 parts by weight of solid content excluding the organic solvent in the composition for forming an organic film.
The composition for forming an organic film according to claim 7, wherein the film thickness enhancing polymer includes at least one of the polymers having the following repeating units.

An organic film comprising a cured product of the composition for forming an organic film according to any one of claims 6 to 10.
Applying the composition for forming an organic film according to any one of claims 6 to 10 on a substrate; and
A method of producing an organic film comprising curing the composition for forming an organic film applied on the substrate.
Applying the composition for forming an organic film according to any one of claims 6 to 10 on a substrate;
forming an underlayer film by curing the composition for forming an organic film applied on the substrate;
forming a resist film on the underlayer film;
performing an exposure process on the resist film; and
A pattern forming method comprising forming a resist pattern by performing a development process on the exposed resist film.
The method of claim 13, after forming the resist pattern, etching the underlayer using the resist pattern as a mask to obtain a patterned underlayer, and using the patterned underlayer as a mask. The method further includes etching the substrate to form a pattern on the substrate.
15. The method of claim 14, wherein between forming the underlayer film and forming the resist film, forming an intermediate layer film on the underlayer film, and forming the resist pattern and obtaining the patterned underlayer film. The method further includes the step of etching the intermediate layer film using the resist pattern as a mask to obtain a patterned intermediate layer film.
16. The method of claim 15, wherein the intermediate layer film is made of an inorganic material selected from the group consisting of titanium nitride, titanium oxynitride, silicon oxide, silicon oxynitride, silicon nitride, and combinations thereof.
A semiconductor device manufactured through the pattern forming method according to claim 13.