Solvent-based composition, composition for removing resist, developer composition, and method for forming pattern

Abstract

A solvent-based composition, a composition for removing edge beads from a metal-containing resist, and / or a developer composition of a metal-containing resist, and a method of forming a pattern using the same are provided. The composition includes a polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group; and an organic solvent.

Description

[0001] Cross - reference to related applications

[0002] This application claims the priority and benefit of Korean Patent Application No. 10 - 2024 - 0007650, filed on January 17, 2024, with the Korean Intellectual Property Office, the entire contents of which are hereby incorporated by reference herein. Technical field

[0003] The present disclosure relates to a solvent - based composition, a composition for removing edge beads from a metal - containing resist, a developer composition for a metal - containing resist, and a method of forming a pattern using the composition. Background art

[0004] In recent years, the semiconductor industry has seen a substantially continuous reduction in critical dimensions, which requires new types of high - performance photoresist materials and patterning methods that meet the needs or expectations for processing and patterning increasingly smaller features.

[0005] In addition, with the rapid development of the semiconductor industry in recent years, semiconductor devices are expected or required to have fast operation speeds and large storage capacities. Consistent with this requirement, process technologies for improving the integration, reliability, and response speed of semiconductor devices are being developed or pursued. For example, it is important or desirable to accurately control / implant impurities in the working areas of a silicon substrate and interconnect these areas to form devices and / or ultra - high - density integrated circuits, which can be achieved through a lithography process. For example, it is important or desirable to integrate a lithography process that includes coating a photoresist on a substrate, selectively exposing it to ultraviolet (UV) light (including extreme ultraviolet (EUV)), electron beams, X - rays, and / or the like, and then developing it.

[0006] For example, in the process of forming a photoresist layer, while rotating a silicon substrate, the photoresist is mainly coated on the substrate (e.g., the top surface), but the photoresist may also be coated on the edge and back surface of the substrate, which may generate particles and / or cause pattern defects in subsequent semiconductor processes such as etching and / or ion implantation processes. Therefore, a process of stripping and removing the photoresist coated on the edge and back surface of the silicon substrate using a thinner composition, i.e., an edge bead removal (EBR) process, is performed. The EBR process requires or desires a composition that exhibits excellent or appropriate solubility in the photoresist and effectively removes the remaining beads and photoresist in the substrate without leaving photoresist residues.

[0007] There is also a need or desire to develop a photoresist that can ensure excellent or appropriate etching resistance and resolution in a lithography process, while improving sensitivity and critical dimension (CD) uniformity, and can improve the line edge roughness (LER) characteristics, as well as a developer composition that can achieve these required or desired characteristics. Summary of the Invention

[0008] Aspects according to one or more embodiments are directed to a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist.

[0009] Aspects according to one or more embodiments are directed to a method of forming a pattern using the composition.

[0010] Other aspects will be set forth in part in the description below, and in part will be obvious from the description, or may be learned by practice of the presented embodiments of the disclosure.

[0011] According to one or more embodiments, a composition (e.g., a solvent-based composition) includes a polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group; and an organic solvent. Herein, the solvent-based composition can be a composition for removing edge beads from a metal-containing resist and / or a developer composition for a metal-containing resist.

[0012] According to one or more embodiments, a method of forming a pattern includes: coating a metal-containing photoresist composition on a substrate; coating an edge bead removal composition for removing edge beads from the metal-containing resist along the edge of the substrate to remove edge beads; drying and heating to form a metal-containing photoresist layer on the substrate; exposing the metal-containing photoresist layer; and developing the metal-containing photoresist layer using a developer composition,

[0013] wherein at least one of the edge bead removal composition or the developer composition includes the above composition.

[0014] The composition for removing edge beads from a metal-containing resist according to one or more embodiments reduces the metal-like contamination inherent in the metal-containing resist and removes the resist coated on the edge and back surface of the substrate, thereby meeting the requirements for processing and patterning smaller features.

[0015] The developer composition for a metal-containing resist according to one or more embodiments can achieve excellent or appropriate contrast characteristics, excellent or appropriate sensitivity, and reduced line edge roughness (LER) by minimizing or reducing the defects present in the metal-containing photoresist layer after the exposure process and promoting development. Brief Description of the Drawings

[0016] The above and other aspects, features, and improvements of certain embodiments of the present disclosure will become more apparent from the following description in conjunction with the accompanying drawings, wherein:

[0017] Figure 1 is a schematic diagram of a photoresist coating apparatus.

[0018] Figure 2 is a cross-sectional view schematically showing the process sequence of a method for forming a pattern according to one or more embodiments of the present disclosure.

[0019] Description of Reference Numerals

[0020] 1: Substrate support part

[0021] 2: Spray nozzle

[0022] 10: Photoresist solution

[0023] 12: Edge bead

[0024] 100: Substrate

[0025] 110: Feature layer

[0026] 110P: Feature pattern

[0027] 130P: Photoresist pattern

[0028] OP: Opening

[0029] W: Substrate Detailed Description of Embodiments

[0030] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the accompanying drawings. In the following description of the present disclosure, known functions or structures will not be described in order to clarify the present disclosure.

[0031] In order to clearly illustrate the present disclosure, descriptions and relationships that those of ordinary skill in the art should understand are not provided, and throughout the disclosure, the same or similar configuration elements are designated by the same reference numerals. In addition, since the dimensions and thicknesses of each configuration shown in the drawings are arbitrarily shown for better understanding and convenience of description, the present disclosure is not necessarily limited thereto.

[0032] In the drawings, the thicknesses of layers, films, panels, regions, and / or the like may be exaggerated for clarity. In the drawings, the thicknesses of some layers, regions, and / or the like may be exaggerated for clarity. It will be understood that if (e.g., when) an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element, or intervening elements may also be present.

[0033] In the present disclosure, the term "substituted" means that a hydrogen atom is replaced by the following: deuterium, halogen, hydroxyl, mercapto, cyano, carbonyl, carboxyl, amino, amido, ester, substituted or unsubstituted C1-C30 amino, nitro, substituted or unsubstituted C1-C40 silyl, C1-C30 alkyl, C1-C10 haloalkyl, C1-C10 alkylsilyl, C3-C30 cycloalkyl, C6-C30 aryl, C1-C20 alkoxy or C1-C20 thioether. As used herein, the term "unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being replaced by another substituent.

[0034] In the present disclosure, unless otherwise defined, the term "alkyl" refers to a straight-chain or branched-chain aliphatic hydrocarbon group. The alkyl group can be a "saturated alkyl" that does not contain any double bonds or triple bonds.

[0035] The alkyl group can be a C1-C20 alkyl group. For example, the alkyl group can be a C1-C10 alkyl group or a C1-C6 alkyl group. For example, "C1-C5 alkyl" means that the alkyl chain contains 1 to 5 carbon atoms and can be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0036] Non-limiting examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and / or the like.

[0037] In the chemical formulas described herein, "t-Bu" refers to the tert-butyl group.

[0038] In the present disclosure, if (e.g., when) no other definition is provided, the term "cycloalkyl" refers to a monovalent cyclic aliphatic hydrocarbon group.

[0039] The cycloalkyl group can be a C3-C10 cycloalkyl group, for example, a C3-C8 cycloalkyl group, a C3-C7 cycloalkyl group, or a C3-C6 cycloalkyl group. For example, the cycloalkyl group can be cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, but the present disclosure is not limited thereto.

[0040] In the present disclosure, if (e.g., when) no other definition is provided, the term "heterocycloalkyl" refers to a cycloalkyl group containing at least one heteroatom selected from N, O, S, P, and Si.

[0041] In the present disclosure, if (e.g., when) no other definition is provided, the term "alkenyl" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and can refer to an aliphatic unsaturated alkenyl group containing one or more double bonds.

[0042] In the present disclosure, if (e.g., when) no other definition is provided, the term "alkynyl" refers to a straight-chain or branched-chain aliphatic hydrocarbon group and can refer to an unsaturated alkynyl group containing one or more triple bonds.

[0043] In the present disclosure, the term "aryl" refers to a substituent in which all elements of the cyclic substituent have p-orbitals and these p-orbitals form a conjugated substituent, and may include monocyclic, polycyclic or fused-ring (i.e., rings sharing adjacent carbon atom pairs) functional groups.

[0044] For example, the term "heteroaryl" may refer to an aryl containing at least one heteroatom selected from N, O, S, P, and Si. Two or more heteroaryls may be directly connected by a σ bond, or if (e.g., when) the heteroaryl contains two or more rings, the two or more rings may be fused. If (e.g., when) the heteroaryl is a fused-ring, each ring may contain one to three heteroatoms.

[0045] For example, a substituted or unsubstituted C6-C30 aryl may be a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted anthracenyl, a substituted or unsubstituted phenanthrenyl, a substituted or unsubstituted tetracenyl, a substituted or unsubstituted pyrenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted p-terphenyl, a substituted or unsubstituted m-terphenyl, a substituted or unsubstituted o-terphenyl, a substituted or unsubstituted chrysenyl, a substituted or unsubstituted benzo[a]phenanthrenyl, a substituted or unsubstituted triphenylenyl, a substituted or unsubstituted perylenyl, a substituted or unsubstituted fluorenyl, a substituted or unsubstituted indenyl, and / or its (e.g., any suitable) combination, but the present disclosure is not limited thereto.

[0046] For example, the substituted or unsubstituted C2-C30 heterocyclic group may be a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuryl group, or a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted benzonaphthofuryl group, a substituted or unsubstituted benzonaphthothienyl group, a substituted or unsubstituted benzofuranylfluorene group, a substituted or unsubstituted benzothienylfluorene group, and / or a combination thereof (e.g., any suitable combination), but the present disclosure is not limited thereto.

[0047] Figure 1 is a schematic view showing a photoresist coating apparatus.

[0048] Referring to Figure 1 , a substrate support portion 1 configured to place a substrate W is provided therein (e.g., within a photoresist coating apparatus), and the substrate support portion 1 includes a rotating chuck or a spin coater.

[0049] The substrate support portion 1 rotates in a first direction at a set or predetermined rotational speed to provide a centrifugal force to the substrate W. The spraying nozzle 2 can be positioned above (or on) the substrate support portion 1, but at a position outside the upper portion of the substrate W in the atmospheric region (e.g., the spraying nozzle 2 can be spaced apart from and / or separated from (e.g., separated) the upper surface of the substrate W), such that the spraying nozzle can move toward the upper portion of the substrate W and spray the photoresist solution 10 during the spraying (e.g., action or task) step. Thus, the photoresist solution 10 is coated on the surface of the substrate W by the centrifugal force. Here, when the photoresist solution 10 supplied to the center of the substrate W is coated by diffusing toward the edge of the substrate W by the centrifugal force, a part of the photoresist solution 10 moves to the side surface of the substrate W and the lower surface of the substrate edge.

[0050] For example, in a coating process, a photoresist solution 10 (e.g., mainly) is coated by a spin coating method, in which a set or predetermined amount of the photoresist solution 10 having (e.g., an appropriate) viscosity is supplied to the central portion of a substrate W and gradually diffuses toward the edge of the substrate W by centrifugal force.

[0051] Accordingly, the photoresist is uniformly formed by the rotational movement (e.g., speed) of the substrate support portion.

[0052] This rotation also causes the solvent in the solution (e.g., the photoresist solution 10) to evaporate, thereby gradually increasing its viscosity, resulting in a portion of the photoresist (e.g., a relatively large amount) accumulating at the edge of the substrate under the action of surface tension and even accumulating on the lower surface of the substrate edge, which is referred to as an edge bead 12.

[0053] Hereinafter, a composition for removing an edge bead from a metal-containing resist (e.g., a metal-containing photoresist) and / or a developer composition for a metal-containing resist according to one or more embodiments will be described.

[0054] A composition for removing an edge bead from a metal-containing resist or a developer composition for a metal-containing resist according to one or more embodiments includes: a polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group; and an organic solvent.

[0055] In one or more embodiments, the polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group may be represented by Chemical Formula 1.

[0056] Chemical Formula 1

[0057]

[0058] In Chemical Formula 1,

[0059] A is a substituted or unsubstituted C5 to C50 polycyclic aliphatic hydrocarbon group in which at least two rings are fused, and

[0060] n is an integer of 1 or greater.

[0061] By including a polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group, the sensitivity can be adjusted such that contrast is exhibited with respect to the photoresist layer in a low exposure energy state, thereby further increasing the solubility difference between the exposed area and the unexposed area.

[0062] In the present disclosure, the term "polycyclic aliphatic hydrocarbon compound" refers to a fused ring structure in which two or more rings share one or more pairs of carbon atoms. For example, it may refer to a bridged polycyclic aliphatic hydrocarbon compound having 5 to 50 carbon atoms.

[0063] The polycyclic aliphatic hydrocarbon compound may include, for example, adamantane, norbornane, isonorbornane, tricyclodecane, tetracyclododecane, bicyclo[2,2,1]heptane, and / or the like, but the present disclosure is not limited thereto.

[0064] In one or more embodiments, A may be a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isonorbornyl group, a substituted or unsubstituted tricyclodecyl group, a substituted or unsubstituted tetracyclododecyl group, a substituted or unsubstituted bicyclo[2.2.1]heptyl group, and / or a combination thereof (e.g., any suitable combination).

[0065] As a non-limiting specific example, the polycyclic aliphatic hydrocarbon compound substituted with a carboxyl group may be any one selected from the compounds listed in Group 1.

[0066] Group 1

[0067]

[0068] The polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group may be included in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the composition.

[0069] For example, the polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group may be included in an amount of about 0.5 wt% to about 10 wt% or about 1 wt% to about 10 wt% based on the total weight of the composition.

[0070] The composition for removing edge beads from a metal-containing resist according to the present disclosure may be effective (e.g., particularly effective) in removing the metal-containing resist (e.g., unwanted metal residues such as tin-based metal residues).

[0071] In addition, the developer composition for the metal-containing resist according to the present disclosure minimizes or reduces defects present in the metal-containing photoresist layer after the exposure process and allows for easy development, thereby achieving excellent or suitable pattern characteristics.

[0072] In addition, excellent or suitable sensitivity and reduced line edge roughness (LER) can be achieved.

[0073] In some embodiments, one or more other additives (to be described in more detail later) may be included, and an organic solvent may be included in the balance except for the other components included.

[0074] One or more other additives may be selected from surfactants, dispersants, moisture absorbers, and coupling agents.

[0075] According to some example embodiments, a method of forming a pattern includes a step (e.g., an action or task) of removing edge beads using the above-described composition for removing edge beads from a metal-containing resist. For example, the pattern being fabricated may be a photoresist pattern. For example, the pattern being fabricated may be a negative or negative-type photoresist pattern.

[0076] A method of forming a pattern according to one or more embodiments includes coating a metal-containing resist composition on a substrate, coating the above-described composition for removing edge beads from a metal-containing resist along an edge of the substrate, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer.

[0077] For example, forming a pattern using a metal-containing resist composition may include coating a metal-containing resist composition (forming a thin film on the substrate) on the substrate by spin coating, slot coating, inkjet printing, and / or a similar method, and drying the coated metal-containing resist composition to form a photoresist layer. The metal-containing resist composition may include a tin compound. For example, the tin compound may include at least one of a tin compound containing an organic oxy group or a tin compound containing an organic carbonyl oxy group.

[0078] For example, the metal-containing resist composition may include a metal compound represented by Chemical Formula 2.

[0079] Chemical Formula 2

[0080]

[0081] In Chemical Formula 2,

[0082] R 1 may be selected from 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 C6 to C30 aryl group, and a substituted or unsubstituted C6 to C30 aralkyl group.

[0083] R 2 to R 4 may each independently be 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 C6 to C30 aryl group; a substituted or unsubstituted C6 to C30 aralkyl group; an alkoxy group or an aryloxy group (-OR a , where R amay be a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); a carboxyl group (-O(CO)R b , where R b may be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an alkylamino or dialkylamino group (-NR c R d , where R c and R d may each independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an amido group (-NR e (COR f ), where R e and R f may each independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an amidino group (-NR g C(NR h )R i , where R g , R h and R i may each independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an alkylthio or arylthio group (-SR j , where R jmay be a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination), or a thiocarboxyl group (-S(CO)R k , where R k may be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination), and

[0084] at least one selected from R 2 to R 4 is selected from the following: an alkoxy group and an aryloxy group (-OR a , where R a may be a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); a carboxyl group (-O(CO)R b , where R b may be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an alkylamino group and a dialkylamino group (-NR c R d , where R c and R d may each independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group and / or a combination thereof (e.g., any suitable combination); an amide group (-NR e (COR f ), where R e and R fEach may independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and / or a combination thereof (e.g., any suitable combination); an amidino group (-NR g C(NR h )R i , where R g , R h , and R i may each independently be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and / or a combination thereof (e.g., any suitable combination); an alkylthio group or an arylthio group (-SR j , where R j may be a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and / or a combination thereof (e.g., any suitable combination); and / or a thiocarboxy group (-S(CO)R k , where R k may be hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, and / or a combination thereof (e.g., any suitable combination). That is, at least one selected from R 2 to R 4 is selected from the following: an alkoxy or aryloxy group represented by -OR a , a carboxy group represented by -O(CO)R b , an alkylamino or dialkylamino group represented by -NR c R d , an amido group represented by -NR e (COR f ), an amidino group represented by -NR g C(NR h )R i , an alkylthio or arylthio group represented by -SR j , and a thiocarboxy group represented by -S(CO)R k .

[0085] The metal compound contained in the metal-containing resist composition can be represented by Chemical Formula 3 or Chemical Formula 4.

[0086] Chemical Formula 3

[0087] R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x

[0088] In Chemical Formula 3,

[0089] R 6 can be a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4;

[0090] Chemical Formula 4

[0091] R 7 n Sn m X l Y k

[0092] Wherein, in Chemical Formula 4,

[0093] R 7 can be 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C4 to C30 heteroaryl group, a carbonyl group, an oxiranyl group, an oxetanyl group and / or a combination thereof (e.g., any suitable combination),

[0094] X can be sulfur (S), selenium (Se) or tellurium (Te),

[0095] Y can be -OR m or -OC(=O)R n ,

[0096] wherein R m can be 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 C6 to C30 aryl group and / or a combination thereof (e.g., any suitable combination),

[0097] R nmay be 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 C6 to C30 aryl group and / or a combination thereof (e.g., any suitable combination), and

[0098] n, m, l and k may each independently be an integer from 1 to 20.

[0099] In one or more embodiments, the composition for removing edge beads from a metal-containing resist along the edge of a substrate may be coated (e.g., to form a photoresist layer) while the substrate is rotating at a suitable or appropriate speed (e.g., 500 revolutions per minute or higher).

[0100] Subsequently, a first heat treatment process of heating the substrate on which the photoresist layer is formed is performed. The first heat treatment process may be performed at a temperature of about 80 °C to about 120 °C, in which the solvent is evaporated and the photoresist layer may adhere more firmly to the substrate.

[0101] Then, the photoresist layer is selectively exposed.

[0102] For example, examples of light that may be used in the exposure process may include not only light with a short wavelength (such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm)), but also light with a high energy wavelength, such as extreme ultraviolet light (EUV, wavelength 13.5 nm), electron beam (E-Beam) and / or similar light.

[0103] In some embodiments, the light for exposure may be short wavelength light having a wavelength range of about 5 nm to about 150 nm, as well as light with a high energy wavelength, such as EUV (extreme ultraviolet light, wavelength 13.5 nm), E-Beam (electron beam) and / or similar light.

[0104] In the step of forming a photoresist pattern (e.g., action or task), a negative or negative type pattern may be formed.

[0105] Because a polymer is formed through a crosslinking reaction such as condensation between organometallic compounds, the exposed area of the photoresist layer has a different solubility from the unexposed area of the photoresist layer.

[0106] Then, 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. By performing the second heat treatment process, the exposed area of the photoresist layer becomes difficult to dissolve in the developer.

[0107] For example, by using an organic solvent such as 2-heptanone to dissolve and remove the photoresist layer corresponding to the unexposed area, a photoresist pattern corresponding to a negative image can be completed.

[0108] Examples of the organic solvent contained in the developer composition used in the method of forming a pattern according to one or more embodiments may be, for example, one or more of the following: ketones (such as methyl ethyl ketone, acetone, cyclohexanone, and / or 2-heptanone), alcohols (such as 4-methyl-2-pentanol, 1-butanol, isopropyl alcohol, 1-propanol, and / or methanol), esters (such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone), aromatic compounds (such as benzene, xylene, and / or toluene), and / or a combination thereof (e.g., any suitable combination).

[0109] (A photoresist pattern formed) not only by exposure to light with a short wavelength (such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), or ArF excimer laser (wavelength 193 nm)), but also by exposure to light with high energy (such as EUV (extreme ultraviolet light, wavelength 13.5 nm)) and / or even E-beam (electron beam) can have a width of about 5 nm to about 100 nm. For example, the photoresist pattern can be formed to have a width of about 5 nm to about 90 nm, about 5 nm to about 80 nm, about 5 nm to about 70 nm, about 5 nm to about 60 nm, about 5 nm to about 50 nm, about 5 nm to about 40 nm, about 5 nm to about 30 nm, or about 5 nm to about 20 nm.

[0110] In addition, the photoresist pattern can have a pitch with a half pitch less than or equal to about 50 nm (e.g., less than or equal to 40 nm, less than or equal to 30 nm, less than or equal to 20 nm, or less than or equal to 15 nm), and a line width roughness less than or equal to about 10 nm (e.g., less than or equal to about 5 nm, less than or equal to about 3 nm, or less than or equal to about 2 nm).

[0111] The method of forming a pattern according to one or more embodiments includes coating a metal-containing resist composition on a substrate, removing the edge beads of the metal-containing resist, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing using the aforementioned developer composition for the metal-containing resist.

[0112] Coating the metal-containing resist composition on the substrate is the same as described above.

[0113] Removing the edge beads of the metal-containing resist can be performed by coating an appropriate or suitable amount of (e.g., a generally known) organic solvent or composition for removing edge beads along the edge of the substrate while the substrate is rotating at an appropriate or suitable speed (e.g., 500 revolutions per minute or higher).

[0114] Drying and heating on the substrate to form a metal-containing photoresist layer is the same as described above.

[0115] Exposing the metal-containing photoresist layer is the same as described above.

[0116] A photoresist pattern corresponding to a negative image can be completed by using a developer composition for the aforementioned metal-containing resist to dissolve the photoresist layer corresponding to the unexposed area and then removing the photoresist layer.

[0117] The metal compound contained in the metal-containing resist composition may include at least one of a tin compound containing an organic oxy group or a tin compound containing an organic carbonyl oxy group.

[0118] Specific non-limiting examples of the metal compound contained in the metal-containing resist composition are as described above.

[0119] Hereinafter, a method of forming a pattern by development will be described in more detail with reference to the accompanying drawings.

[0120] Figure 2 is a cross-sectional view showing the process sequence of the method of forming a pattern.

[0121] Referring to Figure 2 in (a) of (for example, the exposed photoresist layer coated on the substrate 100) is developed to form a photoresist pattern 130P.

[0122] In one or more embodiments, the exposed photoresist layer may be developed to remove the unexposed area of the photoresist layer, and a photoresist pattern 130P including the exposed area of the photoresist layer may be formed. The photoresist pattern 130P may include a plurality of openings OP.

[0123] In one or more embodiments, the development of the photoresist layer may be performed by a negative-tone development (NTD) process. Here, a developer composition for the metal-containing photoresist according to one or more embodiments can be used as the developer composition.

[0124] Referring to Figure 2 in (b), the feature layer (for example, the target layer) 110 is processed using the photoresist pattern 130P from Figure 2 the result shown in (a) of.

[0125] For example, the feature layer 110 is processed by one or more suitable processes, which include: etching the feature layer 110 exposed through the openings OP of the photoresist pattern 130P, implanting impurity ions into the feature layer 110, forming an additional film on the feature layer 110 through the openings OP, deforming (for example, removing) a part of the feature layer 110 through the openings OP, and / or similar processes.Figure 2 Part (b) of [reference] shows an example process of processing the feature pattern 110P by etching the feature layer 110 exposed through the opening OP.

[0126] Referring to Figure 2 part (c) of [reference], the photoresist pattern 130P remaining on the feature pattern 110P in the result shown in Figure 2 part (b) is removed. To remove the photoresist pattern 130P, ashing and stripping processes can be used.

[0127] A method of forming a pattern according to one or more embodiments includes: coating a metal-containing resist composition on a substrate, coating the above composition for removing edge beads from the metal-containing resist along the substrate edge, drying and heating to form a metal-containing photoresist layer on the substrate, exposing the metal-containing photoresist layer, and developing the metal-containing photoresist layer using the developer composition of the above metal-containing resist.

[0128] Each (e.g., action or task) step of the method is substantially the same as above, but in the edge bead removal (e.g., action or task) step and the development (e.g., action or task) step, the composition for removing edge beads from the metal-containing resist or the developer composition of the metal-containing resist according to the embodiments of the present disclosure is used synchronously (e.g., simultaneously) to effectively improve the effect of removing edge beads and the solubility of the unexposed area, so as to meet the requirements or desires of processing and patterning smaller features, and as a result, excellent or appropriate contrast characteristics, excellent or appropriate sensitivity, and reduced line edge roughness (LER) are achieved.

[0129] After that, the present disclosure will be described in more detail by examples related to the preparation of the above composition for removing edge beads from the metal-containing resist and the developer composition of the metal-containing resist. However, the technical features of the present disclosure are not limited by the following examples.

[0130] Preparation of Composition / Developer Composition for Removing Edge Beads from Metal-Containing Resist

[0131] Example 1 and Example 2

[0132] According to the compositions shown in Table 1, 1-adamantanecarboxylic acid or bicyclo[2.2.1]heptane-2-carboxylic acid is mixed with propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and then completely dissolved therein by shaking at room temperature (25 °C). Subsequently, the obtained solution is filtered through a PTFE filter material with a pore size of 0.01 micrometer to prepare each final composition.

[0133] Comparative Example 1 to Comparative Example 4

[0134] Each composition was prepared in substantially the same manner as in Example 1, except that the composition was varied as shown in Table 1.

[0135] Table 1

[0136]

[0137] *AdA: 1 - Adamantanecarboxylic acid

[0138] *BCyHepA: Bicyclo[2.2.1]heptane - 2 - carboxylic acid

[0139] *AA: Acetic acid

[0140] *SIA: Salicylic acid

[0141] *PthA: Phthalic acid

[0142] Preparation of the organometallic resist composition

[0143] An organometallic compound having a structural unit 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 to prepare a resist composition.

[0144] Chemical Formula C

[0145]

[0146] Evaluation 1: Evaluation of contrast performance and sensitivity

[0147] The metal - containing resist (PR) composition was spin - coated on an 8 - inch wafer at a speed of 1,500 revolutions per minute for 30 seconds, and then heat - treated at 160 °C for 60 seconds to produce a coated wafer.

[0148] The coated wafer was exposed with a dose of 10 to 55 mJ in a rectangular pattern shape of 1.2 cm × 0.9 cm using a KrF scanner (PAS 5500 / 700D, ASML), and heat - treated at 160 °C for 90 seconds (e.g., to form a metal - containing resist layer), and then a developer composition according to Example 1, Example 2, and Comparative Examples 1 to 4 was applied thereto to develop the metal - containing resist layer, and then, finally, heat - treated at 240 °C for 60 seconds to obtain a patterned wafer. The contrast curve was obtained by measuring the thickness of each exposed area on the patterned wafer, and the contrast performance (γ (contrast)) and sensitivity (D 100 ) were calculated therefrom. The base of log(D 100 / D0) is 10.

[0149] γ (contrast) = 1 / log(D 100 / D0)

[0150] D 100 = The exposure dose at which 100% of the photoresist remains

[0151] D0 = The exposure dose at which the photoresist is completely removed

[0152] Evaluation 2: Measurement of critical dimension (CD)

[0153] The developer is evaluated by injecting the developer during the development process in the coating-exposure-development process for manufacturing a patterned wafer. After the process is completed, a line / space CD pattern is formed on the patterned wafer and then transferred to Hitachi's GC-5000CD-SEM measurement device to measure the critical dimension (CD) size of the region where the mask pattern half pitch is 14 nanometers. The minimum value of the space between lines, i.e., the space CD, is shown in Table 2.

[0154] Table 2

[0155]

[0156] Referring to Table 2, when the developer composition containing a metal-containing photoresist according to the example is applied, excellent or appropriate contrast performance and excellent or appropriate sensitivity characteristics are shown, excellent or appropriate resolution is obtained, and the occurrence of residual resist or bridging is minimized or reduced compared to applying the developer composition containing a metal-containing photoresist according to the comparative example.

[0157] It will be further understood that when used in this specification, the terms "comprising", "including", "include" and / or "containing" specify the presence of the described features, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, elements, components and / or their groups. As used herein, the term "a combination thereof" refers to a mixture, laminate, composite, copolymer, alloy, admixture, reaction product and / or the like of the components.

[0158] As used herein, the term "use" can be considered to be synonymous with the term "utilize" respectively. As used herein, expressions such as "at least one of", "one of" and "selected from", when located after or before a list of elements, modify the entire list of elements rather than a single element of the list. For example, "at least one selected from a, b and c", "at least one of a, b or c" and "at least one of a, b and / or c" can only represent a, only represent b, only represent c, (e.g., simultaneously) both a and b, (e.g., simultaneously) both a and c, (e.g., simultaneously) both b and c, all of a, b and c, or variants thereof.

[0159] As used when describing embodiments of the inventive concept, "may" means "one or more embodiments of the inventive concept".

[0160] As used herein, the terms "about" and similar terms are used as approximate terms and not terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by a person of ordinary skill in the art. "About" as used herein includes the stated value and refers to an acceptable deviation range of the specific value determined by a person of ordinary skill in the art, taking into account the measurements being discussed and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system). For example, "about" may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0161] In addition, any numerical range described herein is intended to include all sub-ranges having the same numerical precision that are contained within the stated range. For example, the range "1.0 to 10.0" is intended to include all sub-ranges (and including) between the minimum value 1.0 and the maximum value 10.0 stated, i.e., having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limitation described herein is intended to include all lower numerical limitations contained therein, and any minimum numerical limitation described in this specification is intended to include all higher numerical limitations contained therein. Accordingly, the applicant reserves the right to amend this specification (including the claims) to expressly recite any sub-ranges that are contained within the ranges expressly recited herein.

[0162] Previously, certain embodiments of the present disclosure have been described and illustrated. However, it will be apparent to a person of ordinary skill in the art that the present disclosure is not limited to the one or more embodiments described, and various modifications and transformations can be made without departing from the spirit and scope of the present disclosure. Accordingly, such modified or transformed embodiments should not be construed as being separate from the technical ideas and aspects of the present disclosure, and the modified embodiments are within the scope of the claims of the present disclosure and their equivalents.

Claims

1. A solvent composition, comprising: A polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group; and An organic solvent, wherein the solvent composition is a composition for removing edge beads from a metal-containing resist or a developer composition for a metal-containing resist.

2. The solvent composition according to claim 1, wherein The polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group is represented by Chemical Formula 1: Chemical Formula 1 Among them, In Chemical Formula 1, A is a substituted or unsubstituted C5 - C50 polycyclic aliphatic hydrocarbon group, where at least two rings are fused, and n is an integer of 1 or greater.

3. The solvent composition according to claim 2, wherein A is a substituted or unsubstituted adamantyl group, a substituted or unsubstituted norbornyl group, a substituted or unsubstituted isonorbornyl group, a substituted or unsubstituted tricyclodecyl group, a substituted or unsubstituted tetracyclododecyl group, a substituted or unsubstituted bicyclo[2.2.1]heptyl group, or a combination thereof.

4. The solvent composition according to claim 1, wherein The polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group is any one selected from the compounds in Group 1: Group 1 5. The solvent composition according to claim 1, wherein Based on the total weight of the solvent composition, the amount of the polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group is 0.1 wt% to 10 wt%.

6. A method of forming a pattern, the method comprising: Coating a metal-containing photoresist composition on a substrate; Coating an edge bead removal composition for removing edge beads from the metal-containing resist along the edge of the substrate to remove edge beads; Drying and heating to form a metal-containing photoresist layer on the substrate; Exposing the metal-containing photoresist layer; and Developing the metal-containing photoresist layer using a developer composition for a metal-containing resist, wherein at least one of the edge bead removal composition or the developer composition is the solvent composition according to claim 1.

7. The method according to claim 6, wherein The metal-containing photoresist composition contains a metal compound, and the metal compound is at least one of a tin compound containing an organic oxy group or a tin compound containing an organic carbonyl oxy group.

8. The method according to claim 6, wherein The metal-containing photoresist composition contains a metal compound, and the metal compound is represented by Chemical Formula 2: Chemical Formula 2 Among them, In Chemical Formula 2, R 2 selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C6-C30 aralkyl, R 2 to R 4 each independently is a substituted or unsubstituted C1-C20 alkyl group; a substituted or unsubstituted C3-C20 cycloalkyl group; a substituted or unsubstituted C2-C20 alkenyl group; a substituted or unsubstituted C2-C20 alkynyl group; a substituted or unsubstituted C6-C30 aryl group; a substituted or unsubstituted C6-C30 aralkyl group; an alkoxy or aryloxy group represented by -OR a wherein R a is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; a carboxyl group represented by -O(CO)R b wherein R b is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an alkylamino or dialkylamino group represented by -NR c R d wherein R c and R d each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an amide group represented by -NR e (COR f ) wherein R e and R f each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an amidino group represented by -NR g C(NR h )R i wherein R g , R h and R i each independently is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group or a combination thereof; an alkylthio group represented by -SR j An alkylthio or arylthio group represented by, where R j is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; or a thiocarboxy group represented by -S(CO)R k where R k is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof; and R 2 to R 4 at least one selected from the following is selected from: alkoxy or aryloxy represented by -OR a carboxy represented by -O(CO)R b alkylamino or dialkylamino represented by -NR c R d amide group represented by -NR e (COR f ) guanidino group represented by -NR g C(NR h )R i alkylthio or arylthio represented by -SR j and thiocarboxy represented by -S(CO)R k wherein.

9. The method according to claim 6, wherein The metal-containing photoresist composition contains a metal compound represented by Chemical Formula 3 or Chemical Formula 4: Chemical Formula 3 R 6 z SnO (2-(z / 2)-(x / 2)) (OH) x , Among them, In Chemical Formula 3, R 6 is a C1 to C31 hydrocarbon group, 0 < z ≤ 2, and 0 < (z + x) ≤ 4; Chemical Formula 4 R 7 n Sn m X l Y k , wherein, in Chemical Formula 4, R 7 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatically unsaturated organic group containing one or more double or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an oxiranyl group, an oxetanyl group, or a combination thereof, X is sulfur, selenium, or tellurium, Y is -OR m or -OC(=O)R n and wherein R m is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, R n is hydrogen, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof, and n, m, l, and k are each independently an integer from 1 to 20.

10. The method according to claim 6, wherein The edge bead removal composition is the solvent composition.

11. The method according to claim 6, wherein The developer composition is the solvent composition.

12. The method according to claim 6, wherein Both the edge bead removal composition and the developer composition are the solvent composition.

13. A composition for removing edge beads from a metal-containing resist, which is the solvent-based composition according to claim 1.

14. A developer composition for a metal-containing resist, which is the solvent-based composition according to claim 1.

15. A solvent-based composition comprising: a polycyclic aliphatic hydrocarbon compound substituted with at least one carboxyl group; and an organic solvent.

16. A method of forming a pattern, the method comprising: coating a metal-containing photoresist composition on a substrate; coating an edge bead removal composition for removing edge beads from the metal-containing resist along an edge of the substrate to remove edge beads; drying and heating to form a metal-containing photoresist layer on the substrate; exposing the metal-containing photoresist layer; and developing the metal-containing photoresist layer using a developer composition for a metal-containing resist, wherein at least one of the edge bead removal composition or the developer composition comprises the solvent-based composition according to claim 15.

17. The method according to claim 16, wherein the edge bead removal composition comprises the solvent-based composition.

18. The method according to claim 16, wherein the developer composition comprises the solvent-based composition.

19. The method according to claim 16, wherein both the edge bead removal composition and the developer composition comprise the solvent-based composition.

20. A composition for removing edge beads from a metal-containing resist, comprising the solvent-based composition according to claim 15.

21. A developer composition for a metal-containing resist, comprising the solvent-based composition according to claim 15.

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