KR20230083593A - Composition for removing edge bead from metal containing resists, and method of forming patterns incouding step of removing edge bead using the composition - Google Patents

Abstract

A composition for removing edge beads of a metal-containing resist containing an organic solvent and a fluorine-containing sulfonimide-based compound, and a pattern forming method including a step of removing edge beads using the composition are provided.

Description

A composition for removing edge beads of a metal-containing resist, and a pattern forming method including an edge bead removal step using the same

The present disclosure relates to a composition for removing an edge bead of a metal-containing resist, and a pattern forming method including a step of removing an edge bead using the composition.

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 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 composition for removing edge beads of a metal-containing resist.

Another embodiment provides a pattern forming method comprising the step of removing edge beads using the composition.

A composition for removing edge beads of a metal-containing resist according to an embodiment includes an organic solvent and a fluorine-containing sulfonimide-based compound.

The fluorine-containing sulfonimide-based compound may be at least one of the compounds represented by Chemical Formula 1 and Chemical Formula 2 below.

[Formula 1] [Formula 2]

In Formula 1 and Formula 2,

R ¹ and R ² are each independently fluorine, a C1 to C20 alkyl group substituted with at least one fluorine, a C2 to C20 alkenyl group substituted with at least one fluorine, a C2 to C20 alkynyl group substituted with at least one fluorine, at least C3 to C20 cycloalkyl group substituted with one fluorine, C3 to C20 cycloalkenyl group substituted with at least one fluorine, C3 to C20 cycloalkynyl group substituted with at least one fluorine, C6 to C20 substituted with at least one fluorine An aryl group, a C1 to C20 heteroaryl group substituted with at least one fluorine, or a combination thereof;

L ¹ is a C1 to C10 alkylene group substituted with at least one fluorine, a C3 to C20 cycloalkylene group substituted with at least one fluorine, a C6 to C20 arylene group substituted with at least one fluorine, or a C3 to C20 cycloalkylene group substituted with at least one fluorine. A C1 to C20 heteroarylene group, or a combination thereof.

The fluorine-containing sulfonimide-based compound may be at least one of the compounds listed in Group I below.

[Group I]

In the group 1 above,

The pKa of the fluorine-containing sulfonimide-based compound may be 5 or less.

The composition for removing edge beads of a metal-containing resist may include 50 to 99.9% by weight of an organic solvent; and 0.1 to 50% by weight of a fluorine-containing sulfonimide-based compound.

The metal compound included in the metal-containing resist may include 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 3 below.

[Formula 3]

In Formula 3,

R ³ 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 ⁴ to R ⁶ 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.

A pattern formation method according to another embodiment includes applying a metal-containing resist composition on a substrate, removing edge beads by applying and cleaning the composition for removing edge beads of a metal-containing resist along the edge of the substrate, A heat treatment step of evaporating the solvent and forming a metal-containing resist film on the substrate, and forming a resist pattern by exposure and development.

The pattern forming method may further include, after exposure and development, removing edge beads by applying and cleaning the composition for removing edge beads of a metal-containing resist along an edge of the substrate.

A composition for removing an edge bead of a metal-containing resist according to an embodiment reduces metal-based contamination inherent in the metal-containing resist to remove the resist applied to the edge and back surface of a substrate, thereby enabling processing and patterning of smaller features. can meet the needs of

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.

In the present description, “substituted” means that a hydrogen atom is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, a C1 to C30 alkyl group , C1 to C10 haloalkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, or cyano group. "Unsubstituted" means that a hydrogen atom remains a hydrogen atom without being replaced by another substituent.

In the present description, "alkyl group" means a straight-chain or branched-chain aliphatic hydrocarbon group unless otherwise defined. An alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds.

The alkyl group may be a C1 to C20 alkyl group. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, and is represented by methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. indicates that it is selected from the group consisting of

The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, means cheating, etc.

In the present description, "cycloalkyl group" means a monovalent cyclic aliphatic hydrocarbon group unless otherwise defined.

In the present description, "alkenyl group" is a straight-chain or branched-chain aliphatic hydrocarbon group, unless otherwise defined, and means an aliphatic unsaturated alkenyl group containing at least one double bond. do.

In the present description, "alkynyl group" is a straight-chain or branched-chain aliphatic hydrocarbon group, unless otherwise defined, and means an aliphatic unsaturated alkynyl group containing at least one triple bond. do.

In the present description, "aryl group" means a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form conjugation, and monocyclic or fused ring polycyclic It contains click (i.e., a ring that divides adjacent pairs of carbon atoms) functional groups.

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 surface of the edge of the substrate do.

That is, in the application 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 composition for removing edge beads of a metal-containing resist according to an embodiment will be described.

A composition for removing edge beads of a metal-containing resist according to an embodiment of the present invention includes an organic solvent and a fluorine-containing sulfonimide-based compound.

The composition for removing edge beads of metal-containing resists includes a fluorine-containing sulfonimide-based compound, and the imide group of the fluorine-containing sulfonimide-based compound forms a chelate bond with the metal-containing resist. By applying it, it is possible to effectively remove resist containing metal.

For example, the fluorine-containing sulfonimide-based compound may be at least one of the compounds represented by Formula 1 and Formula 2 below.

[Formula 1] [Formula 2]

In Formula 1 and Formula 2,

R ¹ and R ² are each independently fluorine, a C1 to C20 alkyl group substituted with at least one fluorine, a C2 to C20 alkenyl group substituted with at least one fluorine, a C2 to C20 alkynyl group substituted with at least one fluorine, at least C3 to C20 cycloalkyl group substituted with one fluorine, C3 to C20 cycloalkenyl group substituted with at least one fluorine, C3 to C20 cycloalkynyl group substituted with at least one fluorine, C6 to C20 substituted with at least one fluorine An aryl group, a C1 to C20 heteroaryl group substituted with at least one fluorine, or a combination thereof;

L ¹ is a C1 to C10 alkylene group substituted with at least one fluorine, a C3 to C20 cycloalkylene group substituted with at least one fluorine, a C6 to C20 arylene group substituted with at least one fluorine, or a C3 to C20 cycloalkylene group substituted with at least one fluorine. A C1 to C20 heteroarylene group, or a combination thereof.

As a specific example, R ¹ and R ² in Formulas 1 and 2 are each independently a C1 to C10 alkyl group substituted with at least one fluorine, a C6 to C20 aryl group substituted with at least one fluorine, or a combination thereof,

L ¹ may be a C1 to C5 alkylene group substituted with at least one fluorine.

For example, the fluorine-containing sulfonimide-based compound may be at least one of the compounds listed in Group I below.

[Group I]

For example, the pKa of the fluorine-containing sulfonimide-based compound may be 5 or less, for example -20 ≤ pKa ≤ 3.

When the pKa of the fluorine-containing sulfonimide-based compound is within the above range, film removal ability may be further improved.

In one embodiment, the composition for removing edge beads of a metal-containing resist may include 50 to 99.9% by weight of an organic solvent and 0.1 to 50% by weight of the aforementioned fluorine-containing sulfonimide-based compound.

In a specific embodiment, the composition for removing edge beads of a metal-containing resist contains 0.1 to 40% by weight, specifically 0.1 to 30% by weight, and more specifically 0.1 to 20% by weight of the above-mentioned fluorine-containing sulfonimide-based compound. can do.

As an example of the organic solvent included in the composition for removing edge beads of a metal-containing resist according to an embodiment, propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), propylene glycol butyl ether (PGBE), ethylene glycol Methyl ether, ethanol, propanol, isobutyl alcohol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, methyl 2-hydroxy-2-methylpropanoate (HBM), gamma butyrolactone (GBL), ethyl 3-ethoxypropanate (EEP), 1-butanol (n-Butanol), ethyl lactate (EL), 4-methyl-2-pentanol (MIBC), dienbutyl ether (DBE) , diisopropyl ether (DIAE), acetylacetone (Acetyl acetone), butylactate (n-Butylactate), 4-methyl-2-pentanol (or may be written as methyl isobutyl carbinol (MIBC)), 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Ethyl, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, 3-ethoxypropionate Methyl, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxy propio nate, ethoxyethoxypropionate, or a mixture thereof, but is not limited thereto.

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

The metal compound included in the metal-containing resist 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 3 below.

[Formula 3]

In Formula 3,

R ³ 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 ⁴ to R ⁶ 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.

Meanwhile, according to another embodiment, a method of forming a pattern including removing edge beads using the above-described composition for removing edge beads of a metal-containing resist may be provided. For example, the fabricated pattern may be a photoresist pattern. More specifically, it may be a negative photoresist pattern.

A pattern forming method according to an embodiment includes applying a metal-containing resist composition on a substrate, removing edge beads by applying and cleaning the composition for removing edge beads of a metal-containing resist along an edge of the substrate, A heat treatment step of evaporating the solvent and forming a metal-containing resist film on the substrate, and forming a resist pattern by exposure and development.

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.

Subsequently, the step of removing the edge bead may be performed by applying the above-described composition for removing edge beads of a metal-containing resist along the edge of the substrate and cleaning it. Specifically, the composition for removing edge beads of a metal-containing resist may be applied to the edge of the substrate. and removing the beads on the edge of the substrate by spinning the substrate at an appropriate speed (eg, 1,000 rpm or more) after the composition for removing the edge beads of the metal-containing resist is transferred. can include

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 layer has a different solubility from the unexposed region of the photoresist layer 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 cleaning by applying a composition for removing edge beads of a metal-containing resist after the exposure and development processes.

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 of a metal-containing resist. However, the technical features of the present invention are not limited by the following examples.

Preparation of Composition for Edge Bead Removal of Metal-Containing Resist

Examples 1 to 6 and Comparative Examples 1 to 5

After putting the components according to the composition of Table 1 in the PP bottle, mixing, shaking at room temperature (25 ℃) to dissolve completely. Then, a composition for removing edge beads was prepared 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 1: Solubility Evaluation

After preparing the solution with the contents shown in Table 1, it was visually evaluated for the absence of precipitation or haze. (○: transparent without precipitation, X: precipitation or haze occurs)

Evaluation 2: Residual tin (Sn) content

On a 4-inch silicon wafer, 10 mL of the photoresist composition containing an organometallic compound according to the above Preparation Example was added, left for 20 seconds, and then spin-coated at a speed of 800 rpm for 30 seconds. On the wafer on which the coating film was formed, 5 mL of each of the edge bead removal compositions obtained from Examples 1 to 6 and Comparative Examples 1 to 5 was injected along the edge, left for 20 seconds, and then at a speed of 1,500 rpm for 20 seconds spin dry Then, for the film quality obtained by heat treatment at 150 ° C. for 60 seconds, the Sn content is confirmed through VPD ICP-MS analysis.

Composition for edge bead removal of metal-containing resists solubility Residual Sn content
(x10 ¹⁰ atoms/cm ² ) compound weight% Solvent (% by weight) Example 1 Bis(trifluoromethanesulfonyl)imide
(pKa: -10.42) 10 Solvent 1 (90) ○ 45 Example 2 One Solvent 2 (99) ○ 73 Example 3 0.1 Solvent 3 (99.9) ○ 85 Example 4 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide
(pKa: -11.6) 10 Solvent 1 (90) ○ 37 Example 5 One Solvent 2 (99) ○ 48 Example 6 0.1 Solvent 3 (99.9) ○ 89 Comparative Example 1 - - Solvent 1 (100) - 7800 Comparative Example 2 Succimide (pKa: 9.5) 10 Solvent 3 (90) ○ 4700 Comparative Example 3 Maleimide (pKa: 10.0) 10 Solvent 1 (90) ○ 5300 Comparative Example 4 Phthalimide (pKa: 8.3) 10 Solvent 3 (90) ○ 2900 Comparative Example 5 Hexafluorosilicic acid
(pKa: 3.2) 3 Solvent 1 (97) X 82

* Solvent 1: Propylene glycol methyl ether acetate (PGMEA)

* Solvent 2: methyl isobutyl carbinol

* Solvent 3: a mixture of 50% by weight of propylene glycol methyl ether acetate, 10% by weight of ethyl lactate and 40% by weight of methyl 2-hydroxy-2-methyl propionate

Referring to Table 1, the compositions for removing edge beads of metal-containing resists according to Examples 1 to 6 have excellent metal removal effects compared to the compositions for removing edge beads of metal-containing resists according to Comparative Examples 1 to 5, It can be confirmed that the reduction of metal can be further promoted.

In the foregoing, although specific embodiments of the present invention have been described and illustrated, 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)

organic solvents, and
A composition for removing edge beads of a metal-containing resist, comprising a fluorine-containing sulfonimide-based compound.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the fluorine-containing sulfonimide-based compound is at least one of compounds represented by Formulas 1 and 2 below:
[Formula 1] [Formula 2]

In Formula 1 and Formula 2,
R ¹ and R ² are each independently fluorine, a C1 to C20 alkyl group substituted with at least one fluorine, a C2 to C20 alkenyl group substituted with at least one fluorine, a C2 to C20 alkynyl group substituted with at least one fluorine, at least C3 to C20 cycloalkyl group substituted with one fluorine, C3 to C20 cycloalkenyl group substituted with at least one fluorine, C3 to C20 cycloalkynyl group substituted with at least one fluorine, C6 to C20 substituted with at least one fluorine An aryl group, a C1 to C20 heteroaryl group substituted with at least one fluorine, or a combination thereof;
L ¹ is a C1 to C10 alkylene group substituted with at least one fluorine, a C3 to C20 cycloalkylene group substituted with at least one fluorine, a C6 to C20 arylene group substituted with at least one fluorine, or a C3 to C20 cycloalkylene group substituted with at least one fluorine. A C1 to C20 heteroarylene group, or a combination thereof.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the fluorine-containing sulfonimide-based compound is at least one of the compounds listed in Group I below:
[Group I]

.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the fluorine-containing sulfonimide-based compound has a pKa of 5 or less.
In paragraph 1,
50 to 99.9% by weight of the organic solvent; and
A composition for removing edge beads of metal-containing resists, comprising 0.1 to 50% by weight of the fluorine-containing sulfonimide-based compound.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the metal compound included in the metal-containing resist includes at least one of an alkyl tin oxo group and an alkyl tin carboxyl group.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the metal compound included in the metal-containing resist is represented by Formula 3 below:
[Formula 3]

In Formula 3,
R ³ 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 ⁴ to R ⁶ 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.
applying a metal-containing resist composition on a substrate;
removing edge beads by applying and cleaning the composition for removing edge beads of a metal-containing resist according to any one of claims 1 to 7 along an edge of the substrate;
a heat treatment step of evaporating the solvent and forming a metal-containing resist film on the substrate;
and
Forming a resist pattern by exposure and development
Pattern forming method comprising a.
In paragraph 8,
After the exposure and development processes, the method of forming a pattern further comprising the step of cleaning by applying a composition for removing edge beads of a metal-containing resist.

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