KR20230014620A - Method of forming patterns - Google Patents

Abstract

The present invention relates to a method for forming a pattern, which comprises: a step of applying a metal-containing resist composition onto a substrate; a step of applying a composition for removing edge beads along the edge of the substrate; a heat treatment step of performing drying and heating to form a metal-containing resist film on the substrate; and a step of performing exposure and development to form a resist pattern. The composition for removing edge beads includes at least one additive selected from a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent.

Description

Pattern forming method {METHOD OF FORMING PATTERNS}

The present disclosure relates to a method of forming a pattern comprising applying an edge bead removal composition to reduce metal contamination along a wafer edge.

In recent years, the semiconductor industry has been accompanied by a continual reduction in critical dimensions, which requires new types of high-performance photoresist materials and patterning methods to meet the demands of processing and patterning of increasingly smaller features. there is.

In addition, with the recent rapid development of the semiconductor industry, operating speed and large-capacity storage capacity of semiconductor devices are required, and process technologies for improving integration, reliability, and response speed of semiconductor devices are being developed in line with these demands. In particular, it is important to accurately control/inject impurities into the working regions of the silicon substrate, and to interconnect these regions to form devices and ultra-high-density integrated circuits, which is possible through a photolithography process. That is, it has become important to consider the integration of a photolithography process that includes applying a photoresist on a substrate, selectively exposing it by irradiating ultraviolet rays (including extreme ultraviolet rays), electron beams, or X-rays, and then developing.

In particular, in the process of forming a photoresist layer, resist is applied on the substrate while rotating the silicon substrate. or cause pattern defects. Therefore, a process of stripping and removing the photoresist applied to the edge and back surface of the silicon substrate using a thinner composition, that is, an EBR (EDGE BEAD REMOVAL) process is performed. The EBR process requires a composition that exhibits excellent solubility in photoresist and does not generate resist residue by effectively removing beads and photoresist remaining on the substrate.

One embodiment provides a pattern formation method, in particular, a pattern formation method including applying a composition for removing edge beads.

A pattern forming method according to an embodiment includes applying a metal-containing resist composition on a substrate; applying a composition for removing edge beads along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; and exposing and developing to form a resist pattern;

The edge bead removal composition may include at least one additive selected from a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent.

The composition for removing edge beads may include 0.01 to 50% by weight of the additive and 50 to 99.99% by weight of the organic solvent.

After the exposure and development processes, a step of applying a composition for removing edge beads may be further included.

The phosphorous acid compound is phosphonic acid, methyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, hexyl phosphonic acid, n-octyl phosphonic acid, tetradecyl phosphonic acid, octadecyl phosphonic acid, phenyl phosphonic acid, vinyl phosphonic acid, aminomethyl Phosphonic acid, methylenediamine tetra methylene phosphonic acid, ethylenediamine tetra methylene phosphonic acid, 1-amino 1-phosphonooctyl phosphonic acid, etidronic acid, 2-aminoethyl phosphonic acid, 3-aminopropyl phosphonic acid, 6-hydroxy It may be at least one of hexyl phosphonic acid, decyl phosphonic acid, methylene diphosphonic acid, nitrilotrimethylene triphosphonic acid, 1H, 1H, 2H, 2H-perfluorooctanephosphonic acid, or a combination thereof.

The hypophosphorous acid-based compound is phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, bis (hydroxymethyl) phosphinic acid, p- (3-aminopropyl) It may be at least one of -p-butylphosphinic acid or a combination thereof.

The hydroxamic acid compounds include formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2-fluorobenzo Hydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4-nitrobenzohyd It may be at least one kind of loxamic acid or a combination thereof.

The moisture content of the composition for removing edge beads may be 1,000 ppm or less.

The metal-containing resist composition may include a metal compound including at least one of an alkyl tin oxo group and an alkyl tin carboxyl group.

A metal compound included in the metal-containing resist may be represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C2 to C20 alkynyl group a C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R ^a -OR ^b (where R ^a is a substituted or unsubstituted C1 to C20 alkylene group, and R ^b is a substituted or unsubstituted It is selected from C1 to C20 alkyl groups),

R ² to R ⁴ are each independently selected from -OR ^c or -OC(=O)R ^d ;

R ^c is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted A C6 to C30 aryl group, or a combination thereof,

R ^d is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C2 to C20 alkynyl group, An unsubstituted C6 to C30 aryl group, or a combination thereof.

The pattern formation method according to an embodiment can reduce metal-based contamination inherent in metal-containing resists to meet the needs of processing and patterning of smaller features by removing the resist applied to the edge and back surface of the substrate. .

1 is a schematic diagram showing a photoresist coating device.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present description, descriptions of already known functions or configurations will be omitted to clarify the gist of the present description.

In order to clearly describe the description, parts irrelevant to the description have been omitted, and the same reference numerals are used for the same or similar components throughout the specification. In addition, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, the present description is not necessarily limited to those shown.

In the drawings, the thickness is shown enlarged to clearly express the various layers and regions. Also, in the drawings, the thicknesses of some layers and regions are exaggerated for convenience of description. When a part such as a layer, film, region, plate, etc. is said to be "on" or "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where there is another part in between.

1 is a schematic diagram showing a photoresist coating device.

Referring to FIG. 1 , a substrate support 1 on which a substrate W is placed is provided, and the substrate support 1 includes a spin chuck or a spin coater.

The substrate support 1 rotates in a first direction at a predetermined rotational speed and provides centrifugal force to the substrate W. A spray nozzle 2 is positioned on the substrate support 1, and the spray nozzle 2 is located in a waiting area away from the top of the substrate W, and moves to the top of the substrate in the step of supplying the photoresist solution 10. ) can be injected. Accordingly, the photoresist solution 10 is applied to the surface of the substrate by the centrifugal force. At this time, the photoresist solution 10 supplied to the center of the substrate (W) is applied while spreading to the edge of the substrate (W) by centrifugal force, and a part of it is moved to the side surface of the substrate and the lower edge of the substrate. do.

That is, in the coating process, the photoresist solution 10 is mainly applied by a spin coating method. A predetermined amount of the viscous photoresist solution 10 is supplied to the central portion of the substrate W and gradually spread toward the edge of the substrate by centrifugal force. I'm going.

Accordingly, the thickness of the photoresist is formed evenly by the rotational speed of the substrate support.

However, as the solvent evaporates, the viscosity gradually increases, and a relatively large amount of photoresist is accumulated on the edge of the substrate due to the action of surface tension. edge bead) (12).

Hereinafter, a pattern forming method according to an embodiment will be described.

A pattern formation method according to an embodiment includes applying a metal-containing resist composition on a substrate, applying a composition for removing edge beads along an edge of the substrate, drying and heating to form a metal-containing resist film on the substrate It includes a heat treatment step, and a step of forming a resist pattern by exposing and developing.

More specifically, the step of forming a pattern using a metal-containing resist composition includes a process of applying the metal-containing resist composition on a substrate on which a thin film is formed by spin coating, slit coating, inkjet printing, or the like, and the applied metal-containing resist composition. A process of forming a photoresist film by drying may be included. The metal-containing resist composition may include a tin-based compound, and for example, the tin-based compound may include at least one of an alkyl tin oxo group and an alkyl tin carboxyl group.

For example, the metal compound included in the metal-containing resist may be represented by Chemical Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C2 to C20 alkynyl group a C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R ^a -OR ^b (where R ^a is a substituted or unsubstituted C1 to C20 alkylene group, and R ^b is a substituted or unsubstituted It is selected from C1 to C20 alkyl groups),

R ² to R ⁴ are each independently selected from -OR ^c or -OC(=O)R ^d ;

R ^c is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted A C6 to C30 aryl group, or a combination thereof,

R ^d is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C2 to C20 alkynyl group, An unsubstituted C6 to C30 aryl group, or a combination thereof.

In one embodiment, the edge bead removal composition may include at least one additive selected from a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent.

The composition for removing edge beads may include 0.01 to 50% by weight of the additive and 50 to 99.99% by weight of the organic solvent.

In a specific embodiment, the composition for removing the edge bead may include 0.1 to 40% by weight, specifically 0.5 to 30% by weight, and more specifically 1 to 20% by weight of the additive.

As an example of the organic solvent included in the composition for removing edge beads according to an embodiment, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol methyl ether, di Ethyl glycol ethyl methyl ether, dipropyl glycol dimethyl ether, ethanol, 2-butoxyethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butyl Ren carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone , tetrahydrofuran, dimethylsulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl- 2-hydroxy-2-methylpropanate (HBM), gamma butyrolactone (GBL), 1-butanol (n-Butanol), ethyl lactate (EL), dienbutyl ether (DBE), diisopropyl ether (DIAE), Acetyl acetone, n-Butylactate, 4-methyl-2-pentanol (alternatively it can be written as methyl isobutyl carbinol (MIBC)), 1-methoxy-2 -Propanol, 1-ethoxy-2-propanol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxyethyl propionate, 2-hydroxy-2-methylethylpropionate, ethoxyacetic acid Ethyl, hydroxyethyl acetate, 2-hydroxy-3-methylbutanoate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate, methylpyruvate ( methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, methoxybenzene methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxy propionate, ethoxyethoxypropionate, or mixtures thereof, but are not limited thereto. not.

The edge bead removal composition according to the present invention may be particularly effective for removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

For example, the phosphorous acid compound is phosphonic acid, methyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, hexyl phosphonic acid, n-octyl phosphonic acid, tetradecyl phosphonic acid, octadecyl phosphonic acid, phenyl phosphonic acid, vinyl phosphonic acid , aminomethyl phosphonic acid, methylenediamine tetra methylene phosphonic acid, ethylenediamine tetra methylene phosphonic acid, 1-amino 1-phosphonooctyl phosphonic acid, etidronic acid, 2-aminoethyl phosphonic acid, 3-aminopropyl phosphonic acid, 6 - It may be at least one of hydroxyhexyl phosphonic acid, decyl phosphonic acid, methylene diphosphonic acid, nitrilotrimethylene triphosphonic acid, 1H, 1H, 2H, 2H-perfluorooctanephosphonic acid, or a combination thereof.

For example, the hypophosphorous acid-based compound is phosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, bis(4-methoxyphenyl)phosphinic acid, bis(hydroxymethyl)phosphinic acid, p-(3- It may be at least one of aminopropyl)-p-butylphosphinic acid or a combination thereof.

For example, the hydroxamic acid-based compound is formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2- Fluorobenzohydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4- It may be at least one type of nitrobenzohydroxamic acid or a combination thereof.

As the composition for removing edge beads includes at least one additive selected from a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, the moisture content in the composition may be 1,000 ppm or less.

When the water content in the composition exceeds 1,000 ppm, film quality deformation may occur due to hydration in the photoresist contact area.

For example, when phosphoric acid or the like is included as an additive, the moisture content exceeds 1,000 ppm, which may cause film quality deformation due to hydration at the photoresist contact portion.

Specifically, the step of applying the composition for removing the edge bead may include applying an appropriate amount of the composition for removing the edge bead along the edge of the substrate while spinning the substrate at an appropriate speed (eg, 500 rpm or more) can

Subsequently, a first heat treatment process of heating the substrate on which the photoresist film is formed is performed. The first heat treatment process may be performed at a temperature of about 80° C. to about 120° C. In this process, the solvent is evaporated and the photoresist film may be more firmly adhered to the substrate.

Then, the photoresist film is selectively exposed to light.

For example, examples of the light usable in the exposure process include light having a short wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm) as well as EUV (wavelength 193 nm). Extreme UltraViolet (wavelength 13.5 nm), light having a high energy wavelength such as E-Beam (electron beam), etc. may be mentioned.

More specifically, light for exposure according to an embodiment may be short-wavelength light having a wavelength range of 5 nm to 150 nm, and light having a high-energy wavelength such as EUV (Extreme Ultraviolet; wavelength 13.5 nm) or E-Beam (electron beam). can

In the forming of the photoresist pattern, a negative pattern may be formed.

The exposed region of the photoresist film has a different solubility from the unexposed region of the photoresist film as a polymer is formed by a crosslinking reaction such as condensation between organometallic compounds.

Subsequently, a second heat treatment process is performed on the substrate. The second heat treatment process may be performed at a temperature of about 90 °C to about 200 °C. As a result of performing the second heat treatment process, the exposed region of the photoresist film becomes difficult to dissolve in a developing solution.

Specifically, the photoresist pattern corresponding to the negative tone image may be completed by dissolving the photoresist film corresponding to the unexposed area using an organic solvent such as 2-heptanone and then removing the film. .

The developer used in the pattern formation method according to one embodiment may be an organic solvent, for example, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 4-methyl-2-propanol, 1 Alcohols such as butanol, isopropanol, 1-propanol and methanol, esters such as propylene glycol methyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate and butyrolactone, aromatics such as benzene, xylene and toluene compounds, or combinations thereof.

In addition, the pattern forming method may further include applying a composition for removing edge beads after the exposure and development processes. 500 rpm or more) and applying an appropriate amount of the composition for removing edge beads along the edge of the substrate while spinning.

As described above, as well as light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), The photoresist pattern formed by exposure to light having high energy such as an E-Beam (electron beam) may have a width of 5 nm to 100 nm. For example, the photoresist pattern is 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm , may be formed with a width of 5 nm to 20 nm thickness.

On the other hand, the photoresist pattern has a half-pitch of about 50 nm or less, for example 40 nm or less, for example 30 nm or less, for example 20 nm or less, for example 15 nm or less, and about It may have a pitch having a line width roughness of 10 nm or less, about 5 nm or less, about 3 nm or less, or about 2 nm or less.

Hereinafter, the present invention will be described in more detail through examples related to the preparation of the above-described composition for removing edge beads. However, the technical features of the present invention are not limited by the following examples.

Examples 1 to 5 and Comparative Examples 1 to 3: Preparation of composition for removing edge beads

After mixing the additives and the solvent according to the composition shown in Table 1 below, they are completely dissolved by shaking at room temperature (25° C.). Thereafter, the composition for removing the final edge bead was obtained by passing through a filter made of PTFE having a pore size of 1 μm.

Preparation Example: Preparation of organometallic photoresist composition

After dissolving an organometallic compound having the structure of Chemical Formula C at a concentration of 1 wt% in 4-methyl-2-pentanol, the photoresist composition was filtered through a 0.1 μm PTFE syringe filter. manufactured.

[Formula C]

Evaluation: Residual Tin (Sn) Content

On a 4-inch silicon wafer, 1.0 mL of the organic metal-containing photoresist composition according to the above Preparation Example was added, left for 20 seconds, and then spin-coated at a speed of 1,500 rpm for 30 seconds. While rotating the wafer on which the coating film was formed at a speed of 800 rpm, 6.5 mL of the composition for removing edge beads obtained from Examples 1 to 5 and Comparative Examples 1 to 3 was injected along the edge, respectively, and after spin coating for 3 seconds, a speed of 1,500 rpm Rotate and dry for 25 seconds. The steps of adding the composition for removing the edge bead, spin coating, and drying are repeated three times. After baking at 150 ° C. for 60 seconds, the Sn content is confirmed through VPD ICP-MS analysis.

Composition for edge bead removal Residual Sn content
(x10 ¹⁰ atoms/cm ² ) Additives (% by weight) Solvent (% by weight)
[Mixing ratio (w/w)] Example 1 Phenyl Phosphonic Acid (10) MIBC(90) 31 Example 2 Phosphonic acid (10) PGMEA(90) 33 Example 3 Vinyl Phosphonic Acid (10) PGMEA(90) 26 Example 4 Acetohydroxamic acid (1) PGMEA/PGME(99) [7:3] 45 Example 5 Salicylhydroxamic acid (1) PGMEA(99) 48 Comparative Example 1 glycolic acid (10) PGMEA/PGME(90)[5:5] 350 Comparative Example 2 glycolic acid (10) PGMEA(90) 220 Comparative Example 3 phosphoric acid (10) PGMEA(90) 290

Referring to Table 1, the edge bead removal compositions according to Examples 1 to 5 have excellent metal removal effects compared to the edge bead removal compositions according to Comparative Examples 1 to 3, so that the reduction of residual metal can be further promoted. can confirm that there is

In the foregoing, although specific embodiments of the present invention have been described and shown, the present invention is not limited to the described embodiments, and it is common knowledge in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. It is self-evident to those who have Therefore, such modifications or variations should not be individually understood from the technical spirit or viewpoint of the present invention, and modified embodiments should fall within the scope of the claims of the present invention.

1: substrate support 2: spray nozzle
10: photoresist solution 12: edge bead

Claims (9)

applying a metal-containing resist composition on a substrate;
applying a composition for removing edge beads along the edge of the substrate;
a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; and
Forming a resist pattern by exposure and development
including,
The pattern forming method of claim 1 , wherein the composition for removing edge beads includes at least one additive selected from a phosphorous acid-based compound, a hypophosphorous acid-based compound, a sulfurous acid-based compound, and a hydroxamic acid-based compound, and an organic solvent. In paragraph 1,
The composition for removing edge beads includes 0.01 to 50% by weight of the additive and 50 to 99.99% by weight of the organic solvent. In paragraph 1,
After the exposure and development processes, the pattern forming method further comprising the step of applying a composition for removing edge beads. In paragraph 1,
The phosphorous acid compound is phosphonic acid, methyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, hexyl phosphonic acid, n-octyl phosphonic acid, tetradecyl phosphonic acid, octadecyl phosphonic acid, phenyl phosphonic acid, vinyl phosphonic acid, aminomethyl Phosphonic acid, methylenediamine tetra methylene phosphonic acid, ethylenediamine tetra methylene phosphonic acid, 1-amino 1-phosphonooctyl phosphonic acid, etidronic acid, 2-aminoethyl phosphonic acid, 3-aminopropyl phosphonic acid, 6-hydroxy At least one of hexyl phosphonic acid, decyl phosphonic acid, methylene diphosphonic acid, nitrilotrimethylene triphosphonic acid, 1H, 1H, 2H, 2H-perfluorooctanephosphonic acid, or a combination thereof. In paragraph 1,
The hypophosphorous acid-based compound is diphenylphosphinic acid, bis (4-methoxyphenyl) phosphinic acid, phosphinic acid, bis (hydroxymethyl) phosphinic acid, phenylphosphinic acid, p- (3-aminopropyl) -At least one of p-butylphosphinic acid or a combination thereof, a pattern forming method. In paragraph 1,
The hydroxamic acid compound includes formohydroxamic acid, acetohydroxamic acid, benzohydroxamic acid, salicylhydroxamic acid, 2-aminobenzohydroxamic acid, 2-chlorobenzohydroxamic acid, 2-fluorobenzo Hydroxamic acid, 2-nitrobenzohydroxamic acid, 3-nitrobenzohydroxamic acid, 4-aminobenzohydroxamic acid, 4-chlorobenzohydroxamic acid, 4-fluorobenzohydroxamic acid, 4-nitrobenzohyd A pattern forming method, which is at least one of loxamic acid or a combination thereof. In paragraph 1,
The water content of the edge bead removal composition is 1,000 ppm or less, pattern forming method. In paragraph 1,
wherein the metal-containing resist composition comprises a metal compound comprising at least one of an alkyl tin oxo group and an alkyl tin carboxyl group. In paragraph 8,
The metal compound is represented by Formula 1, a pattern forming method:
[Formula 1]

In Formula 1,
R ¹ is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a substituted or unsubstituted C2 to C20 alkynyl group a C6 to C30 aryl group, a substituted or unsubstituted C6 or C30 arylalkyl group, and -R ^a -OR ^b (where R ^a is a substituted or unsubstituted C1 to C20 alkylene group, and R ^b is a substituted or unsubstituted It is selected from C1 to C20 alkyl groups),
R ² to R ⁴ are each independently selected from -OR ^c or -OC(=O)R ^d ;
R ^c is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C2 to C20 alkynyl group A C6 to C30 aryl group, or a combination thereof,
R ^d is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C2 to C20 alkynyl group, An unsubstituted C6 to C30 aryl group, or a combination thereof.

Images