CN117616109A

CN117616109A - Composition for removing edge bead from metal-containing resist and method for forming pattern

Info

Publication number: CN117616109A
Application number: CN202280047982.2A
Authority: CN
Inventors: 李旻映; 文炯朗; 许伦旼; 金旼秀; 金荣权; 金宰贤; 禹昌秀
Original assignee: Samsung SDI Co Ltd
Current assignee: Samsung SDI Co Ltd
Priority date: 2021-07-08
Filing date: 2022-06-27
Publication date: 2024-02-27

Abstract

A composition for removing edge beads from a metal-containing resist and a method of forming a pattern are provided, the method comprising the step of removing edge beads using the composition, and the composition comprising an organic solvent and a cyclic compound substituted with at least one hydroxyl (-OH), wherein the cyclic compound has a carbon number of 5 to 30, and the cyclic compound has at least one double bond in the ring.

Description

Composition for removing edge bead from metal-containing resist and method for forming pattern

Technical Field

The present disclosure relates to a composition for removing edge beads (edge beads) from a metal-containing resist and a method of forming a pattern, the method comprising the step of removing edge beads using the composition.

Background

In recent years, the semiconductor industry has been accompanied by a continual decrease in critical dimensions (critical dimension), and such a decrease in dimensions requires new high performance photoresist materials and patterning methods that meet the demands for processing and patterning smaller and smaller features (features).

In addition, with the recent rapid progress of the semiconductor industry, a semiconductor device is required to have a rapid operation speed and a large storage capacity, and according to such a requirement, a process technology for improving the integration, reliability and response speed of the semiconductor device is being developed. Specifically, it is important to accurately control/implant impurities in the working regions of the silicon substrate and interconnect these regions to form devices and ultra-high density integrated circuits, which can be achieved by a photolithography process (photolithographic process). In other words, it is important to integrate the photolithography process including the following operations: a photoresist is coated on a substrate, selectively exposed to Ultraviolet (UV), including extreme ultraviolet (extreme ultraviolet, EUV), electron Beam (E-Beam), X-ray, or the like, and then developed.

Specifically, in a process of forming a photoresist layer, a resist is coated on a substrate mainly while rotating the silicon substrate, wherein the resist is coated on the edge and rear surface of the substrate, which may cause an indentation (or pattern defect) in a subsequent semiconductor process such as an etching process and an ion implantation process. Thus, a process of stripping and removing photoresist coated on the edge and rear surface of the silicon substrate using the thinner composition (thinner composition), i.e., a bead removal (edge bead removal, EBR) process, is performed. The EBR process requires a composition that exhibits excellent solubility (solubility) to photoresist and effectively removes beads and photoresist remaining in the substrate without generating resist residues.

Disclosure of Invention

[ problem to be solved by the invention ]

One embodiment provides a composition for removing edge beads from a metal-containing resist.

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

[ means of solving the problems ]

The composition for removing side beads from a metal-containing resist according to one embodiment includes an organic solvent and a cyclic compound (cyclic compound) substituted with at least one hydroxyl group (-OH), wherein the cyclic compound has 5 to 30 carbon numbers, and the cyclic compound has at least one double bond in a ring (ring).

The cyclic compound may be substituted with one or two hydroxyl groups (-OH).

The cyclic compound may have 5 to 20 carbon atoms.

The cyclic compound may have 5 to 10 carbon atoms.

The cyclic compound may be represented by any one of chemical formulas 1 to 3.

In the chemical formulas 1 to 3,

R ¹ to R ¹⁷ Each independently is hydrogen, halogen, hydroxy, amino (amino group), substituted or unsubstituted C1 to C30 amino (amine group), substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl, and

R ¹ to R ⁶ At least one of R ⁷ To R ¹¹ At least one of R ¹² To R ¹⁷ At least one of which is a hydroxyl group.

The cyclic compound may be selected from the formulas of group 1.

Group 1

In the group 1 of the two-way set,

R ¹ to R ¹⁷ Each independently is hydrogen, halogen, an amine group, a substituted or unsubstituted C1 to C30 amine group, a substituted or unsubstituted C1 to C10 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The cyclic compound may be selected from the group 2 compounds.

Group 2

The composition for removing edge beads from a metal-containing resist may include 50 to 99.99 wt% of the organic solvent; and 0.01 to 50% by weight of the cyclic compound.

The metal compound included in the metal-containing resist may include at least one of an alkyl tin pendant oxy group and an alkyl tin carboxyl group.

The metal compound contained in the metal-containing resist may be represented by chemical formula 4.

[ chemical formula 4]

In the chemical formula 4, the chemical formula is shown in the drawing,

R ¹⁸ selected from the group consisting of substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 or C30 aralkyl, and-R ^a -O-R ^b (wherein R is ^a Is a substituted or unsubstituted C1 to C20 alkylene group, and R ^b A substituted or unsubstituted C1 to C20 alkyl group),

R ¹⁹ to R ²¹ Each independently selected from-OR ^c or-OC (=o) R ^d ，

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

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

A method of forming a pattern according to another embodiment includes: coating a metal-containing resist composition on a substrate; coating the edge of the substrate with the aforementioned composition for removing edge beads from the metal-containing resist; drying and heating the resultant to form a metal-containing resist film on the substrate; and exposing and developing the resultant to form a resist pattern.

The method of forming a pattern may further include: after exposure and development, the aforementioned composition for removing edge beads from the metal-containing resist is applied along the edges of the substrate.

[ Effect of the invention ]

The composition for removing edge beads from a metal-containing resist according to one embodiment reduces metal-based contamination inherent in metal-containing resists and removes resist coated on the edge and back surfaces of the substrate, thereby meeting the need to process and pattern smaller features.

Drawings

Fig. 1 is a schematic view of a photoresist coating apparatus.

[ description of the marks ]

1 substrate supporting portion

2 nozzle

10 Photoresist solution

12 side bead

Detailed Description

Hereinafter, embodiments of the present invention are described in detail with reference to the accompanying drawings. In the following description of the present disclosure, well-known functions or constructions will not be set forth in order to elucidate the disclosure.

For purposes of clarity of illustration of the present disclosure, the descriptions and relationships are omitted, and the same or similar configuration elements are denoted by the same reference numerals throughout the disclosure. Further, the present disclosure is not necessarily limited thereto, as the size and thickness of each configuration shown in the drawings is arbitrarily shown for better understanding and ease of illustration.

In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. In the drawings, the thickness of a portion of a layer or region, etc., is exaggerated for clarity. It will be understood that when an element (e.g., a layer, film, region, or substrate) is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present.

In the present disclosure, "substituted" means that a hydrogen atom is replaced with deuterium, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amino, nitro, substituted or unsubstituted C1 to C40 silyl, C1 to C30 alkyl, C1 to C10 haloalkyl, C1 to C10 alkylsilyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C1 to C20 alkoxy, or cyano. "unsubstituted" means that a hydrogen atom remains as a hydrogen atom and is not replaced by another substituent.

In the present disclosure, when definition is not otherwise provided, the term "cyclic compound" refers to a compound having a structure in which terminal atoms constituting a molecule are linked to each other to form a ring, and it may be classified into "carbocyclic compound (carbocyclic compound)" and "heterocyclic compound (heterocyclic compound)" according to the type of atoms forming the ring.

"carbocyclic compound" refers to a compound in which the ring-forming atom is carbon only.

"heterocyclic compound" refers to a compound that includes heteroatoms in addition to the carbon atoms that form the ring.

Heteroatoms that may be included in the "heterocyclic compound" may include, but are not limited to, N, O, S, P, si and the like.

In the present disclosure, the term "alkyl group" means a straight or branched chain aliphatic hydrocarbon group unless otherwise defined. The alkyl group may be a "saturated alkyl group (saturated alkyl group)" which 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, C1 to C4 alkyl means that the alkyl chain contains 1 to 4 carbon atoms and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl and third butyl.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

In the present disclosure, when the definition is not otherwise provided, the term "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group.

In the present disclosure, when no definition is otherwise provided, the term "alkenyl group" is a straight or branched chain aliphatic hydrocarbon group and refers to an aliphatic unsaturated alkenyl group unsaturated alkenyl group containing one or more double bonds.

In the present disclosure, when no definition is otherwise provided, the term "alkynyl" is a straight or branched chain aliphatic hydrocarbon group and refers to an unsaturated alkynyl group (unsaturated alkynyl group) containing one or more triple bonds.

In the present disclosure, "aryl" means a substituent in which all elements of a cyclic substituent have a p-orbital (p-orbital), and the p-orbitals form a conjugate and can include single or fused ring multiple ring (i.e., rings sharing pairs of adjacent carbon atoms) functional groups.

Fig. 1 is a schematic view of a photoresist coating apparatus.

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

The substrate supporting portion (1) rotates in a first direction at a predetermined rotation speed and provides a centrifugal force to the substrate (W). A nozzle (2) is provided on the substrate supporting part (1), and the nozzle (2) is located in an atmospheric pressure region (atm) offset from an upper part of the substrate (W) and moves to the upper part of the substrate during the solution supplying step to spray the photoresist solution (10). Thus, the photoresist solution (10) is coated on the surface of the substrate by centrifugal force. At this time, the photoresist solution (10) supplied to the center of the substrate (W) is coated while being spread to the edge of the substrate (W) by centrifugal force, and a portion thereof is moved to the side surface of the substrate and the lower surface of the edge of the substrate.

That is, in the coating process, the photoresist solution (10) is mainly coated by the spin coating method (spin coating method). By supplying a predetermined amount of viscous photoresist solution (10) to the center of the substrate (W), it gradually diffuses toward the edge of the substrate by centrifugal force.

Therefore, the thickness of the photoresist is formed to be uniform (flat) by the rotation speed of the substrate supporting portion.

However, as the solvent evaporates, the viscosity gradually increases, and a relatively large amount of photoresist accumulates on the edge of the substrate under the effect of the surface tension. More seriously, the photoresist accumulates to the lower surface of the edge of the substrate, which is referred to as edge bead (12).

Hereinafter, a composition for removing edge beads from a metal-containing resist according to one embodiment is set forth.

The composition for removing edge beads from a metal-containing resist according to an embodiment of the present invention includes an organic solvent and a cyclic compound substituted with at least one hydroxyl group (-OH), wherein the cyclic compound has a carbon number of 5 to 30 and the cyclic compound has at least one double bond in a ring.

"double bonds" include at least one in the ring, and do not include forms that continuously include double bonds due to the nature of the rigid structure of the cyclic compound. "having at least one double bond in the ring" means that one double bond is contained by at least one single bond.

The composition for removing the edge bead from the metal-containing resist includes a cyclic compound substituted with a hydroxyl group (-OH), and the hydroxyl group (-OH) coordinates with the metal-containing resist, and the metal-containing resist can be effectively removed by coating the composition including the cyclic compound.

For example, the cyclic compound may be substituted with one or two hydroxyl groups (-OH).

The cyclic compound may have 5 to 20 carbon atoms, for example 5 to 10 carbon atoms.

For example, the cyclic compound may have 6 to 20 carbon atoms.

As a specific example, the cyclic compound may have 6 to 10 carbon atoms.

For example, the cyclic compound may be represented by any one of chemical formulas 1 to 3.

In the chemical formulas 1 to 3,

R ¹ to R ¹⁷ Each independently is hydrogen, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amino, substituted or unsubstituted C1 to C10 alkyl, or substituted or unsubstituted C6 to C20 aryl, and

As a specific example, the cyclic compound may be selected from the chemical formulas of group 1.

Group 1

In the group 1 of the two-way set,

For example, the cyclic compound may be selected from the group 2 compounds.

Group 2

In exemplary embodiments, the composition for removing edge beads from a metal-containing resist may include 50 to 99.99 wt% of the organic solvent and 0.01 to 50 wt% of the aforementioned cyclic compound.

In a specific embodiment, the composition for removing edge beads from a metal-containing resist may comprise the aforementioned cyclic compound in an amount of 0.05 wt.% to 40 wt.% (specifically, 0.5 wt.% to 30 wt.%, or more specifically, about 1 wt.% to 20 wt.%) of the composition.

According to one embodiment, the organic solvent included in the composition for removing edge beads from a metal-containing resist may be, for example, propylene glycol methyl ether (propylene glycol methyl ether, PGME), propylene glycol methyl ether acetate (propylene glycol methyl ether acetate, PGMEA), propylene glycol butyl ether (propylene glycol butyl ether, PGBE), ethylene glycol methyl ether, diethyl glycol ethyl methyl ether, dipropylene glycol dimethyl ether, ethanol, 2-butoxyethanol, N-propanol, isopropanol, N-butanol, isobutanol, hexanol, ethylene glycol, propylene glycol, heptanone, propylene carbonate, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisoamyl ether, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3-dimethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclohexanone methyl-2-hydroxy-2-methylpropionate (HBM), γ -butyrolactone (gamma butyrolactone), GBL), 1-butanol (N-butanol), ethyl Lactate (EL), diene Butyl Ether (DBE), diisopropyl ether (diisopropyl ether, DIAE), acetylacetone, 4-methyl-2-pentenol (or called methyl isobutyl carbinol (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-methylethyl propionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate (n-butyl lactate), methyl 2-hydroxyisobutyrate (methyl-2-hydroxy-isobutyrate), methoxyphenyl, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures thereof, but are not limited thereto.

The composition for removing edge beads from a metal-containing resist according to the present invention is particularly effective in removing metal-containing resist, more specifically, removing undesirable metal residues such as tin-based metal residues.

For example, the metal compound included in the metal-containing resist may be represented by chemical formula 4.

[ chemical formula 4]

In the chemical formula 4, the chemical formula is shown in the drawing,

R ¹⁹ to R ²¹ 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 unsubstitutedC2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, or a combination thereof, and

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

Also, according to another embodiment, a method of forming a pattern includes the step of removing edge beads using the aforementioned composition for removing edge beads from a metal-containing resist. For example, the pattern fabricated may be a photoresist pattern. More specifically, it may be a negative photoresist pattern (negative-type photoresist pattern).

The method of forming a pattern according to one embodiment includes: coating a metal-containing resist composition on a substrate; coating the edge of the substrate with the aforementioned composition for removing edge beads from the metal-containing resist; drying and heating the resultant to form a metal-containing resist film on the substrate; and exposing and developing the resultant to form a resist pattern.

More specifically, forming a pattern using the metal-containing resist composition may include: coating a 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 drying the coated metal-containing resist composition to form a photoresist film. The metal-containing resist composition can include a tin-based compound, which can include at least one of an alkyl tin pendant oxy group and an alkyl tin carboxyl group, for example.

More specifically, the aforementioned composition for removing edge beads from a metal-containing resist may be applied along the edge of the substrate while the substrate is rotated at a suitable speed (e.g., 500 revolutions per minute (revolutions per minute, rpm) or greater than 500 revolutions per minute).

Subsequently, a first heat treatment process of heating the substrate on which the photoresist film is formed is performed. The first thermal treatment process may be performed at a temperature of about 80 ℃ to about 120 ℃, and in such a process, the solvent is evaporated, and the photoresist film may be more firmly bonded to the substrate.

And the photoresist film is selectively exposed.

Examples of light that can be used in the exposure process may include, for example, not only light having a short wavelength such as i-line (wavelength 365 nm), krF excimer laser (wavelength 248 nm), arF excimer laser (wavelength 193 nm), but also EUV (light having a high energy wavelength such as EUV (extreme ultraviolet, wavelength 13.5 nm), E-Beam (electron Beam), and the like.

More specifically, the light for exposure according to one embodiment may be short wavelength light having a wavelength range of about 5 nm to about 150 nm and light having a high energy wavelength such as EUV (extreme ultraviolet, wavelength 13.5 nm), E-Beam (electron Beam), or the like.

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

The exposed areas of the photoresist film have a solubility that is different from the solubility of the unexposed areas of the photoresist film because the polymer is formed by a crosslinking reaction (e.g., condensation between organometallic compounds).

Then, a second thermal treatment process is performed on the substrate. The second thermal treatment process may be performed at a temperature of about 90 ℃ to about 200 ℃. By performing the second thermal treatment process, the exposed areas of the photoresist film become difficult to dissolve in the developing solution.

Specifically, a photoresist pattern corresponding to the negative tone image (negative tone image) can be completed by dissolving and removing the photoresist film corresponding to the unexposed region using an organic solvent (e.g., 2-heptanone).

The developing solution used in the method of forming a pattern according to the embodiment may be an organic solvent, for example, ketones (e.g., methyl ethyl ketone, acetone, cyclohexanone, or 2-heptanone), alcohols (e.g., 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, or methanol), esters (e.g., propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl acetate, or butyrolactone), aromatic compounds (e.g., benzene, xylene, or toluene), or a combination thereof.

In addition, the method of forming a pattern may further comprise coating the composition for removing edge beads from the metal-containing resist after exposure and development. In particular, the method may include coating a suitable amount of the composition for removing edge beads from the metal-containing resist along an edge of the substrate while rotating the substrate at a suitable speed (e.g., 500 revolutions per minute or greater than 500 revolutions per minute).

As described above, a photoresist pattern formed by exposing not only light having a wavelength such as i-line (wavelength 365 nm), krF excimer laser (wavelength 248 nm), arF excimer laser (wavelength 193 nm) but also EUV (extreme ultraviolet; wavelength 13.5 nm), and also light having high energy such as E-Beam (electron Beam) may have a thickness width (thickness width) of about 5 nm to about 100 nm. For example, the photoresist pattern may be formed to have a thickness width of 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, or 5 nm to 20 nm.

In another aspect, the photoresist pattern may have a half pitch (half-pitch) of a pitch (pitch) of less than or equal to about 50 nanometers, such as less than or equal to 40 nanometers, such as less than or equal to 30 nanometers, such as less than or equal to 20 nanometers, such as less than or equal to 15 nanometers, and the photoresist pattern may have a line width roughness (line width roughness) of less than or equal to about 10 nanometers, less than or equal to about 5 nanometers, less than or equal to about 3 nanometers, or less than or equal to about 2 nanometers.

Hereinafter, the present invention will be described in more detail by way of examples related to the preparation of the aforementioned composition for removing edge beads from metal-containing resists. However, technical features of the present invention are not limited by the following examples.

Preparation of a composition for removal of edge beads containing Metal resists

Example 1

The cyclic compound represented by chemical formula a was mixed with Propylene Glycol Methyl Ether Acetate (PGMEA) as a solvent in the composition shown in table 1, and then completely dissolved by shaking (shaking) at room temperature (25 ℃). The final composition was then obtained by passing through a Polytetrafluoroethylene (PTFE) filter having a pore size (pore size) of 1 micron.

[ chemical formula A ]

Example 2

A composition was obtained in the same manner as in example 1, except that the cyclic compound represented by chemical formula B and methyl isobutyl carbinol (MIBC) as a solvent were used.

[ chemical formula B ]

Comparative example 1

A composition was obtained in the same manner as in example 1, except that glycerin was used instead of the compound of formula a.

Comparative example 2

A composition was obtained in the same manner as in example 1, except that acetic acid was used instead of the compound of formula a.

Comparative example 3

A composition was obtained in the same manner as in example 1, except that acetoxime was used instead of the compound of formula a.

Comparative example 4

A composition was obtained in the same manner as in example 1, except that tetra-n-butylammonium fluoride, TBAF was used instead of the compound of formula a.

Preparation example: preparation of organometallic-containing photoresist compositions

The organometallic compound having the structure of chemical formula C was dissolved in 4-methyl-2-pentanol at a concentration of 1 wt% and then filtered through a 0.1-micron PTFE syringe filter, thereby obtaining a photoresist composition.

[ chemical formula C ]

Evaluation: evaluation of residual film thickness (Strip Test) and evaluation of Sn residual amount before development

1.0 ml of the photoresist composition containing the organometallic compound according to the preparation example was cast on a 6 inch silicon wafer, allowed to stand for 20 seconds, and then spin coated at 800 rpm for 30 seconds. Then, the thickness of the coating film obtained by heat treatment at 180 ℃ for 60 seconds was measured by ellipsometry. 10 ml of each of the compositions for removing edge beads prepared in example 1, example 2 and comparative examples 1 to 4 was added along the edge of the wafer on which the coating film was formed, spin-coated for 5 seconds, and then dried while rotating at a speed of 1,500 rpm. Then, the thickness of each film obtained by heat treatment at 150 ℃ for 60 seconds was re-measured by the ellipsometry, and the thickness variation before the edge bead removal process and after the edge bead removal process was checked and evaluated according to the following criteria. Vapor phase split inductively coupled plasma mass spectrometry (Vapour Phase Decomposition Inductively Coupled Plasma-Mass spectrometry, VPD ICP-MS) analysis was performed to confirm the Sn residual amount, and the results are shown in table 1.

* Residual thickness less than 2 angstroms: o, residual thickness greater than 2 angstrom: x is X

(Table 1)

Referring to table 1, the compositions for removing edge beads from metal-containing resists according to examples 1 and 2 exhibited more improved metal removal effect and further promoted reduction of residual metals than the compositions for removing edge beads from metal-containing resists according to comparative examples 1 to 4.

In the foregoing, certain embodiments of the invention have been described and illustrated, however, it will be apparent to those skilled in the art that the invention is not limited to the embodiments described, and that various modifications and alterations can be made without departing from the spirit and scope of the invention. Therefore, the modified or altered embodiments themselves may not be understood separately from the technical idea and embodiments of the present invention, and the modified embodiments are within the scope of the claims of the present invention.

Claims

1. A composition for removing edge beads from a metal-containing resist comprising:

an organic solvent; and

a cyclic compound substituted with at least one hydroxyl (-OH),

wherein the cyclic compound has a carbon number of 5 to 30, and

the cyclic compound has at least one double bond in the ring.

2. The composition of claim 1, wherein

The cyclic compound is substituted with one or two hydroxyl groups (-OH).

3. The composition of claim 1, wherein

The cyclic compound has 5 to 20 carbon atoms.

4. The composition of claim 1, wherein

The cyclic compound has 5 to 10 carbon atoms.

5. The composition of claim 1, wherein

The cyclic compound is represented by any one of chemical formulas 1 to 3:

wherein, in chemical formulas 1 to 3,

6. The composition of claim 1, wherein

The cyclic compound is selected from the chemical formulas of group 1:

group 1

Wherein, in group 1,

7. The composition of claim 1, wherein

The cyclic compound is selected from the group consisting of compounds of group 2:

group 2

8. The composition of claim 1, wherein

The cyclic compound is contained in an amount of 0.01 to 50% by weight, and the organic solvent is contained in an amount of 50 to 99.99% by weight.

9. The composition of claim 1, wherein

The metal compound included in the metal-containing resist includes at least one of an alkyl tin side oxygen group (alkyl tin oxo group) and an alkyl tin carboxyl group (alkyl tin carboxyl group).

10. The composition of claim 1, wherein

The metal compound contained in the metal-containing resist is represented by chemical formula 4:

[ chemical formula 4]

Wherein, in the chemical formula 4,

R ¹⁸ selected from the group consisting of substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C2 to C20 alkenyl, substituted or unsubstituted C2 to C20 alkynyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C6 to C30 aralkyl, and R ^a -O-R ^b (wherein R is ^a Is a substituted or unsubstituted C1 to C20 alkylene group, and R ^b A substituted or unsubstituted C1 to C20 alkyl group),

R ¹⁹ to R ²¹ Each independently selected from-OR ^c or-OC (=o) R ^d ，

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

11. A method of forming a pattern comprising

Coating a metal-containing resist composition on a substrate;

coating the composition for removing edge beads from the metal-containing resist according to any one of claims 1 to 10 along an edge of the substrate;

drying and heating the metal-containing resist composition to form a metal-containing resist film on the substrate; and

exposure and development are performed to form a resist pattern.

12. The method of claim 11, wherein the method further comprises:

after exposure and the developing, the composition for removing the edge bead from the metal-containing resist is coated along the edge of the substrate.