KR20230009291A - 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

Provided are a composition for removing an edge bead from metal containing resists, which contains an organic solvent and a heptagonal ring compound substituted with at least one hydroxyl group (-OH), wherein the heptagonal ring compound has at least two double bonds in the ring, and a pattern forming method including an edge bead removal step using the same.

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 heptagonal ring compound substituted with at least one hydroxyl group (—OH), wherein the heptagonal ring compound contains at least two has two double bonds.

The heptagonal ring compound may be substituted with one or two hydroxyl groups (—OH).

The heptagonal ring compound may have three double bonds.

The heptagonal ring compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, an amino 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. ego,

At least one of R ¹ to R ⁶ is a hydroxyl group.

The heptagonal ring compound may be selected from the chemical formulas listed in Group 1 below.

[Group 1]

[Formula 1-1] [Formula 1-2] [Formula 1-3]

In the group 1 above,

R ¹ to R ⁶ are each independently hydrogen, halogen, amino group, substituted or unsubstituted C1 to C30 amine group, substituted or unsubstituted C1 to C10 alkyl group, or substituted or unsubstituted C6 to C20 aryl group.

The heptagonal ring compound may be 2-hydroxy-2,4,6-cycloheptatrien-1-one.

The composition for removing edge beads of a metal-containing resist may include 50 to 99.99% by weight of an organic solvent; and 0.01 to 50% by weight of a heptagonal ring 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 ⁷ 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, 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 ⁸ to R ¹⁰ 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 the steps of applying a metal-containing resist composition on a substrate, applying the above-described composition for removing edge beads of a metal-containing resist along the edge of the substrate, drying and heating the substrate A heat treatment step of forming a metal-containing resist film on the surface, and a step of forming a resist pattern by exposure and development.

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

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, unless otherwise defined, the term "heptad ring compound" means a compound having a structure in which terminal atoms constituting a molecule are connected to each other to form a heptagonal ring, depending on the type of atoms forming the ring. It can be classified into 'carbocyclic compounds' and 'heterocyclic compounds'.

The 'carbocyclic compound' refers to a compound in which only carbon atoms form a ring.

The 'heterocyclic compound' refers to a compound in which an atom forming a ring also contains a heteroatom other than carbon.

Heteroatoms that may be contained in the 'heterocyclic compound' include N, O, S, P, Si, and the like, but are not limited thereto.

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 heptagonal ring compound substituted with at least one hydroxyl group (-OH), wherein the heptagonal ring compound is a ring It has at least two double bonds in it.

At least two of the "double bonds" are included in the ring, and due to the nature of the rigid structure of the heptagonal ring compound, forms in which double bonds are continuously included are excluded, and 'having at least two double bonds in the ring' means that two double bonds are involved via at least one single bond.

The composition for removing the edge beads of the metal-containing resist includes a heptagonal ring compound substituted with a hydroxyl group (-OH), and the hydroxyl group (-OH) forms a coordinate bond with the metal-containing resist, By applying a composition including the same, it is possible to effectively remove the metal-containing resist.

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

The heptagonal ring compound may have three double bonds.

For example, the heptagonal ring compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1 and Formula 2,

R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, an amino 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. ego,

At least one of R ¹ to R ⁶ is a hydroxyl group.

As a specific example, the heptagonal ring compound may be selected from the chemical formulas listed in Group 1 below.

[Group 1]

[Formula 1-1] [Formula 1-2] [Formula 1-3]

In the group 1 above,

R ¹ to R ⁶ are each independently hydrogen, halogen, amino group, substituted or unsubstituted C1 to C30 amine group, substituted or unsubstituted C1 to C10 alkyl group, or substituted or unsubstituted C6 to C20 aryl group.

For example, the heptagonal ring compound is 2-hydroxy-2,4,6-cycloheptatrien-1-one (2-Hydroxy-2,4,6-cycloheptatrien-1-one, or Tropolone) ) can be.

In one embodiment, the composition for removing edge beads of a metal-containing resist may include 50 to 99.99% by weight of an organic solvent and 0.01 to 50% by weight of the above-mentioned heptagonal ring compound.

In a specific embodiment, the composition for removing edge beads of a metal-containing resist may include 0.05 to 40% by weight, specifically 0.5 to 30% by weight, and more specifically 1 to 20% by weight of the above-mentioned heptagonal ring compound. .

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, diethyl 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, butylene carbonate, diethyl ether, dibutyl ether, ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diisopentyl ether, xylene, acetone, methyl ethyl ketone, Methylisobutylketone, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, acetonitrile, diacetone alcohol, 3,3-dimethyl-2-butanone, N-methyl-2-pyrrolidone, dimethylacetamide, cyclo Hexanone 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-methylethyl propionate , ethyl ethoxyacetate, ethylhydroxyacetate, 2-hydroxy-3-methylmethylbutanoate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxyethylpropionate, 3-ethoxymethylpropionate , methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate yrate), methoxybenzene, n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, ethoxyethoxypropionate, or mixtures 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 ⁷ 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, 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 ⁸ to R ¹⁰ 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 the steps of applying a metal-containing resist composition on a substrate, applying the above-described composition for removing edge beads of a metal-containing resist along an edge of the substrate, drying and heating the substrate A heat treatment step of forming a metal-containing resist film on the surface, and a step of 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 applying the above-described composition for removing edge beads of a metal-containing resist may be performed, and specifically, while rotating the substrate at an appropriate speed (eg, 500 rpm or more), the metal-containing resist along the edge of the substrate may be rotated. A step of applying an appropriate amount of a composition for removing edge beads may be included.

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 monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, benzene, xylene, toluene, etc. aromatic compounds, or combinations thereof.

In addition, the pattern forming method may further include applying a composition for removing edge beads of a metal-containing resist after the exposure and development processes,

Specifically, the method may include applying an appropriate amount of the composition for removing edge beads of the metal-containing resist along the edge of the substrate while spinning the substrate at an appropriate speed (eg, 500 rpm or more).

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

Example 1

10wt% of 2-Hydroxy-2,4,6-cycloheptatrien-1-one (Tropolone) and 90wt% of PGMEA were put in a PP bottle and stirred for 12 hours to prepare a composition for removing edge beads.

Example 2

A composition for removing edge beads was prepared in the same manner as in Preparation Example 1, except that 5 wt% of 2-Hydroxy-2,4,6-cycloheptatrien-1-one was used.

Example 3

A composition for removing edge beads was prepared in the same manner as in Preparation Example 1, except that 40 wt% of 2-Hydroxy-2,4,6-cycloheptatrien-1-one was used.

Comparative Example 1

A composition for removing edge beads was prepared in the same manner as in Preparation Example 1, except that 10 wt% of glycerol was used instead of 2-Hydroxy-2,4,6-cycloheptatrien-1-one.

Comparative Example 2

A composition for removing edge beads was prepared in the same manner as in Preparation Example 1, except that 10 wt% of acetic acid was used instead of 2-Hydroxy-2,4,6-cycloheptatrien-1-one.

Comparative Example 3

A composition for removing edge beads was prepared in the same manner as in Preparation Example 1, except that 10 wt% of TBAF (Tetrabutylammonium fluoride) was used instead of 2-Hydroxy-2,4,6-cycloheptatrien-1-one.

Preparation Example: Preparation of organometallic photoresist composition

After dissolving an organometallic compound having a structure of 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: Residual film thickness evaluation (Strip test) and Sn residual amount evaluation before development

On a 6-inch silicon wafer, 1.0 mL of the photoresist composition containing an organometallic compound according to the above preparation was added, and after standing for 20 seconds, spin coating was performed at a speed of 800 rpm for 30 seconds. Then, the thickness of the resist film obtained by baking at 180 ° C. for 60 seconds is measured by ellipsometry. While rotating the wafer on which the resist film was formed at a speed of 800 rpm, 10 mL of each of the compositions for removing edge beads prepared from Examples 1 to 3 and Comparative Examples 1 to 3 was added along the edge and spin-coated for 5 seconds, Rotate at a speed of 1,500 rpm and dry. Subsequently, the thickness of the film obtained by baking at 150 ° C for 60 seconds was re-measured by ellipsometry to confirm the thickness change before and after the edge bead removal process, and evaluated according to the following criteria. ^st residual amount) was confirmed, and the results are shown in Table 1.

* In the case of residual thickness less than 2Å: ○, in the case of more than 2Å: X

Evaluation 2: Visual evaluation of stain on the back side

As in Evaluation 1, the surface stains of the wafer on which the resist film was formed through the edge bead removal process were confirmed using the KMAC-ST400DLX equipment, and at the same time, the stains on the back side of the substrate were the stains before and after the heat treatment at 150 ° C for 60 seconds. Check visually. The notation standards are as follows.

* No stains before/after heat treatment: ○, stains remain but disappear after heat treatment: △, stains after heat treatment: X

Evaluation 3: Evaluation of Sn residual amount after development (2 ^nd residual amount)

As in Evaluation 1, the wafer on which the resist film was formed through the edge bead removal process was exposed in a 1: 1 L/S pattern with an e-Beam lithography system (JBX-9300FS, JEOL Co.), followed by heat treatment at 170 ° C. for 60 seconds, A composition for removing edge beads prepared from Examples 1 to 3 and Comparative Examples 1 to 3 for a wafer obtained by heat treatment at 150 ° C. for 60 seconds after development with a propylene glycol methyl ether acetate (PGMEA) developer. After processing again under the same process conditions, the Sn residual amount ( ^2nd residual amount) of the edge portion was confirmed by TXRF, and the results are shown in Table 1.

Residual film after strip back side stain
(visual evaluation) before development
Sn residual amount
(1 ^st remaining)
(x10 ¹⁰ atoms/cm ² ) after developing
Sn residual amount
( ^2nd residual amount)
(x10 ¹⁰ atoms/cm ² ) Example 1 ○ ○ 18 34 Example 2 ○ ○ 40 50 Example 3 ○ ○ 8 12 Comparative Example 1 X △ 3700 640 Comparative Example 2 X ○ 1100 375 Comparative Example 3 X X 5300 971

Referring to Table 1, the compositions for removing edge beads of metal-containing resists according to Examples 1 to 3 have excellent metal removal effects compared to the compositions for removing edge beads of metal-containing resists according to Comparative Examples 1 to 3, 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 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 (11)

organic solvents, and
It includes a heptagonal ring compound substituted with at least one hydroxyl group (-OH),
The heptagonal ring compound has at least two double bonds in the ring, a composition for removing edge beads of a metal-containing resist.
In paragraph 1,
Wherein the heptagonal ring compound is substituted with one or two hydroxyl groups (—OH), a composition for removing edge beads of a metal-containing resist.
In paragraph 1,
The heptagonal ring compound has three double bonds, a composition for removing edge beads of a metal-containing resist.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the heptagonal ring compound is represented by Formula 1 below:
[Formula 1]

In Formula 1,
R ¹ to R ⁶ are each independently hydrogen, halogen, a hydroxyl group, an amino 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. ego,
At least one of R ¹ to R ⁶ is a hydroxyl group.
In paragraph 1,
A composition for removing edge beads of a metal-containing resist, wherein the heptagonal ring compound is one selected from the formulas listed in Group 1 below:
[Group 1]
[Formula 1-1] [Formula 1-2] [Formula 1-3]

In the group 1 above,
R ¹ to R ⁶ are each independently hydrogen, halogen, amino group, substituted or unsubstituted C1 to C30 amine group, substituted or unsubstituted C1 to C10 alkyl group, or substituted or unsubstituted C6 to C20 aryl group.
In paragraph 1,
Edge bead of metal-containing resist, wherein the heptagonal ring compound is 2-hydroxy-2,4,6-cycloheptatrien-1-one composition for removal.
In paragraph 1,
50 to 99.99% by weight of the organic solvent; and
A composition for removing edge beads of a metal-containing resist, comprising 0.01 to 50% by weight of the heptagonal ring 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 ⁷ 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, 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 ⁸ to R ¹⁰ 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;
applying the composition for removing edge beads of a metal-containing resist according to any one of claims 1 to 9 along an 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
Pattern forming method comprising a.
In paragraph 10,
After the exposure and development processes, the pattern forming method further comprising the step of applying a composition for removing edge beads of a metal-containing resist.

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