Composition for removing edge bead from metal-containing resist or developer composition of metal-containing resist, and method of forming patterns using the same

Abstract

To provide a composition for removing edge beads from metal-containing resists or a developer composition of metal-containing resists, and a method of forming patterns using the same.SOLUTION: The present invention provides a composition for removing edge beads from metal-containing resists or a developer composition of metal-containing resists, and a method of forming patterns using the same, wherein the composition includes a C3 to C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups; a mono-carboxylic acid compound; and an organic solvent.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] This description relates to a composition for removing edge beads of a metal-containing resist or a developer composition for a metal-containing resist, and a patterning method using the same.

Background Art

[0002] Recently, in the semiconductor industry, there has been a continuous reduction in critical dimensions. With such dimensional reduction, new types of high-performance photoresist materials and patterning methods have been required to gradually meet the requirements for processing and patterning of smaller features.

[0003] Also, recently, due to the remarkable development of the semiconductor industry, the operating speed and large-capacity storage capacity of semiconductor devices have been required. In line with such requirements, process technologies for improving the integration degree, reliability, and response speed of semiconductor devices have been developed. In particular, it is important to accurately adjust / dope impurities in the active region of a silicon substrate and interconnect such regions to form elements and ultra-high density integrated circuits, which is possible by a photolithography process. That is, it has become important to consider the integration of a photolithography process including 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 it.

[0004] Particularly in the process of forming a photoresist layer, the resist is mainly applied onto the substrate while rotating the silicon substrate. However, in this process, the resist is also applied to the edge and back surface of the substrate, which may cause particles or pattern defects in subsequent semiconductor processes such as etching and ion implantation. 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 carried out. In the EBR process, a composition that exhibits excellent solubility in the photoresist and effectively removes the beads and photoresist remaining on the substrate without generating resist residues is required.

[0005] In addition, it is necessary to develop a photoresist that can ensure excellent etching resistance and resolution in the photolithography process, and at the same time improve sensitivity and CD (critical dimension) uniformity, and can improve the LER (line edge roughness) characteristics, as well as a developer composition that can achieve this.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] One embodiment provides a composition for removing edge beads of a metal-containing resist or a developer composition for a metal-containing resist.

[0007] Another embodiment provides a pattern formation method using the composition.

MEANS FOR SOLVING THE PROBLEMS

[0008] The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to one embodiment includes a C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups; a mono-carboxylic acid compound; and an organic solvent.

[0009] The pattern formation method according to another embodiment includes the steps of applying a metal-containing resist composition on a substrate; an edge bead removal step of applying a composition for removing edge beads of the metal-containing resist along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; an exposure step of exposing the metal-containing photoresist film; and a development step of developing using a developer composition for the metal-containing resist. At least one of the composition for removing edge beads of the metal-containing resist and the developer composition for the metal-containing resist contains the aforementioned composition.

Advantages of the Invention

[0010] The composition for removing edge beads of the metal-containing resist according to one embodiment can reduce the metal-based contamination inherent in the metal-containing resist and remove the resist applied to the edge and back surface of the substrate, thereby satisfying the processing and patterning requirements for smaller features.

[0011] The metal-containing developer composition according to another embodiment has improved detergency and stability over time, facilitating the removal of the photoresist regions changed after the exposure process and enabling the maintenance of the removal performance over a long period. Thereby, excellent exposure characteristics (sensitivity, CD margin, LWR / LER) can be realized.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Modes for Carrying Out the Invention

[0013] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in the description, descriptions of already known functions or configurations are omitted in order to clarify the gist of the description.

[0014] To clarify the description, unnecessary parts are omitted, and the same or similar components throughout the specification are denoted by the same reference numerals. Also, the sizes and thicknesses of the respective configurations shown in the drawings are arbitrarily shown for convenience of explanation, and thus the present description is not necessarily limited to what is shown in the drawings.

[0015] In the drawings, the thickness is enlarged to clearly show a plurality of layers and regions. Also, in the drawings, the thicknesses of some layers and regions are exaggerated for convenience of explanation. When a part such as a layer, film, region, or plate is “on” another part, this includes not only the case where it is “directly on” another part but also the case where there are other parts in between.

[0016] In the present description, “substituted” means that a hydrogen atom is substituted with a deuterium atom, a halogen group, a hydroxy group, a thiol group, a cyano group, a carbonyl group, a carboxyl group, an amino group, an amide group, an ester group, a substituted or unsubstituted C1 - C30 amine group, a nitro group, a substituted or unsubstituted C1 - C40 silyl group, a C1 - C30 alkyl group, a C1 - C10 haloalkyl group, a C1 - C10 alkylsilyl group, a C3 - C30 cycloalkyl group, a C6 - C30 aryl group, a C1 - C20 alkoxy group, or a C1 - C20 sulfide group. “Unsubstituted” means that the hydrogen atom remains as a hydrogen atom without being substituted with other substituents.

[0017] In the present description, the “alkyl group” means a linear or branched aliphatic hydrocarbon group unless otherwise defined. The alkyl group can be a “saturated alkyl group” that does not contain any double bonds or triple bonds.

[0018] The alkyl group may be a C1-C20 alkyl group. More specifically, the alkyl group may be a C1-C10 alkyl group or a C1-C6 alkyl group. For example, a C1-C5 alkyl group means one containing 1 to 5 carbon atoms in the alkyl chain, and is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

[0019] Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group and the like.

[0020] In the chemical formulas described herein, t-Bu means a tert-butyl group.

[0021] In this description, the "cycloalkyl group" means a monovalent cyclic aliphatic hydrocarbon group unless otherwise defined.

[0022] The cycloalkyl group means a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.

[0023] The cycloalkyl group may 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 may be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, but is not limited thereto.

[0024] In this description, the "heterocycloalkyl group" means one containing at least one heteroatom selected from the group consisting of N, O, S, P and Si in the cycloalkyl group unless otherwise defined.

[0025] As used herein, the term "alkenyl group" means an aliphatic hydrocarbon group, linear or branched, having one or more double bonds, and is an aliphatic unsaturated alkenyl group, unless otherwise defined.

[0026] As used herein, the term "alkynyl group" means an aliphatic hydrocarbon group, linear or branched, having one or more triple bonds, and is an aliphatic unsaturated alkynyl group, unless otherwise defined.

[0027] As used herein, the term "aryl group" means a cyclic substituent in which all elements have p-orbitals and these p-orbitals form a conjugation, and includes monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) functional groups.

[0028] As used herein, the term "heteroaryl group" means a group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si within an aryl group. Two or more heteroaryl groups may be directly linked through a sigma bond, or when the heteroaryl group contains two or more rings, the two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

[0029] More specifically, the substituted or unsubstituted C6-C30 aryl group may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted o-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted benzophenanthrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted indenyl group, or a combination thereof, but is not limited thereto.

[0030] More specifically, the substituted or unsubstituted C2-C30 heterocyclic group may be a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl 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 benzofuranyl group, a substituted or unsubstituted benzothiophenyl 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 dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted benzonaphthofuranyl group, a substituted or unsubstituted benzonaphthothiophenyl group, a substituted or unsubstituted benzofuranofluorenyl group, a substituted or unsubstituted benzothiophenefluorenyl group, or a combination thereof, but is not limited thereto.

[0031] FIG. 1 is a schematic diagram showing a photoresist coating apparatus.

[0032] Referring to FIG. 1, a substrate support portion 1 on which a substrate W is placed is provided, and the substrate support portion 1 includes a spin chuck or a spin coater or the like.

[0033] The substrate support portion 1 rotates in the first direction at a predetermined rotational speed and provides a centrifugal force to the substrate W. An injection nozzle 2 is located on the substrate support portion 1. The injection nozzle 2 is located in an air region outside the upper part of the substrate W and can move above the substrate in the solution supply stage to inject the photoresist solution 10. Thereby, the photoresist solution 10 is applied to the substrate surface by the centrifugal force. At this time, the photoresist solution 10 supplied to the center of the substrate W is applied while spreading from the center of the substrate W to the periphery by the centrifugal force, and a part of it moves to the side surface of the substrate and the lower surface of the periphery of the substrate.

[0034] That is, in the coating process, the photoresist solution 10 is mainly applied by the spin coating method. However, a predetermined amount of viscous photoresist solution 10 is supplied to the central portion of the substrate W and gradually diffuses in the direction of the substrate periphery by the centrifugal force.

[0035] Therefore, the thickness of the photoresist is formed flat according to the rotational speed of the substrate support portion.

[0036] However, the solvent evaporates and the viscosity gradually increases. Due to the action of the surface tension, a relatively large amount of photoresist accumulates on the periphery of the substrate. More seriously, the photoresist accumulates up to the lower surface of the periphery of the substrate, which is called an edge bead 12.

[0037] Hereinafter, a composition for removing an edge bead of a metal-containing resist or a developing solution composition of a metal-containing resist according to an embodiment will be described.

[0038] The composition for removing an edge bead of a metal-containing resist or the developing solution composition of a metal-containing resist according to an embodiment of the present invention includes a C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups; a mono-carboxylic acid compound; and an organic solvent.

[0039] An aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups: The mono-carboxylic acid compound may be contained in a weight ratio of 1:0.01 to 1:2.

[0040] As an example, an aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups: The mono-carboxylic acid compound may be contained in a weight ratio of 1:0.1 to 1:2, 1:0.1 to 1:1.5, 1:0.2 to 1:1.5, 1:0.3 to 1:1.5, or 1:0.4 to 1:1.5.

[0041] By mixing and using the aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups and the mono-carboxylic acid compound, the stability of the composition over time is improved, the detergency is increased, various contaminating particles generated by the metal-containing photoresist on the edge or back surface of the substrate are minimized, the removal of the photoresist region changed after the exposure process is facilitated, and the removal performance can be maintained over a long period. Thereby, excellent exposure characteristics (sensitivity, CD margin, LWR / LER) can be realized.

[0042] In this specification, the number of carbon atoms of the aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups does not include the carbon contained in the carboxyl group.

[0043] As an example, in the case of an aliphatic hydrocarbon compound having 3 carbon atoms substituted with at least two carboxyl groups, it means a structure in which at least two carboxyl groups are substituted for an aliphatic hydrocarbon having 3 carbon atoms.

[0044] Specifically, the aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups may be acyclic.

[0045] For example, the aliphatic hydrocarbon compound having 3 to 20 carbon atoms substituted with at least two carboxyl groups may be represented by the following Chemical Formula 1.

[0046] [Chemical formula] In the chemical formula 1, L 1 is at least one of a substituted or unsubstituted C3-C20 alkylene, a substituted or unsubstituted C3-C20 alkenylene, a substituted or unsubstituted C3-C20 alkynylene, a C1-C10 aliphatic hydrocarbon group, and a C6-C12 aromatic hydrocarbon group, a C2-C20 alkylene substituted with at least one of a C1-C10 aliphatic hydrocarbon group and a C6-C12 aromatic hydrocarbon group, a C2-C20 alkenylene substituted with at least one of a C1-C10 aliphatic hydrocarbon group and a C6-C12 aromatic hydrocarbon group, a C3-C20 alkynylene substituted with at least one of a C1-C10 aliphatic hydrocarbon group and a C6-C12 aromatic hydrocarbon group, or a combination thereof. R 1 is an amine group, an amide group, a halogen, a hydroxy group, or a carboxyl group. m1 is an integer of 0 or more.

[0047] The upper limit value of m1 can be the maximum value connectable to L 1 , but m1 can be in the range of, for example, 1 to 10, 1 to 8, 1 to 6, or 1 to 3 within the range of not exceeding the maximum value.

[0048] In one embodiment, the L 1 can be a substituted or unsubstituted propylene, a substituted or unsubstituted butylene, a substituted or unsubstituted pentylene, a substituted or unsubstituted hexylene, a substituted or unsubstituted propenylene, a substituted or unsubstituted butenylene, a substituted or unsubstituted pentenylene, a substituted or unsubstituted hexenylene, an ethylene substituted with a C1-C10 alkyl group, or a combination thereof.

[0049] As a specific example, the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups can be one of the compounds listed in Group 1 below.

[0050] [Chemical formula] As a specific example, the mono-carboxylic acid compound may be one of the compounds listed in Group 2 below.

[0051]

Chemical formula

[0052] For example, the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups and the mono-carboxylic acid compound may be contained in an amount of 0.1 to 25% by weight based on the total weight of the composition.

[0053] The composition for removing edge beads of the metal-containing resist according to the present invention can be particularly effective for removing metal-containing resists, more specifically, undesirable metal residues such as tin-based metal residues.

[0054] In addition, the developer composition of the metal-containing resist according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process and enables easy development, thereby realizing excellent pattern characteristics.

[0055] Moreover, excellent sensitivity and reduced line edge roughness (LER) can also be realized.

[0056] When containing other additives described later, the organic solvent may be contained in the remaining amount excluding the components contained.

[0057] The composition may further contain at least one other additive selected from surfactants, dispersants, moisture absorbers, and coupling agents.

[0058] On the other hand, according to another embodiment, a patterning method may be provided that includes the step of removing edge beads using the above-described composition for removing edge beads of a metal-containing resist. As an example, the produced pattern may be a photoresist pattern. More specifically, it may be a negative photoresist pattern.

[0059] A patterning method according to an embodiment includes a step of applying a metal-containing resist composition on a substrate, a step of applying the above-described composition for removing edge beads of the metal-containing resist along the edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, a step of exposing the metal-containing photoresist film, and a developing step.

[0060] More specifically, the step of forming a pattern using a metal-containing resist composition may include a step of applying the metal-containing resist composition on a substrate on which a thin film is formed by spin coating, slit coating, inkjet printing, etc., and a step of drying the applied metal-containing resist composition to form a photoresist film. The metal-containing resist composition may include a tin-based compound. For example, the tin-based compound may include at least one of an organic oxy group and an organic carbonyloxy group.

[0061] For example, the metal compound contained in the metal-containing resist composition may be represented by Chemical Formula 2 below.

[0062]

Chemical Formula

[0063] Further, the metal compound contained in the metal-containing resist composition may be represented by the following Chemical Formula 3 or Chemical Formula 4.

[0064] [Chemical Formula] In Chemical Formula 3,[[]] R 6 is a C1-C31 hydrocarbyl group, where 0 < z ≦ 2 and 0 < (z + x) ≦ 4; [Chemical Formula] In Chemical Formula 4,[[]] R 7is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur (S), selenium (Se) or tellurium (Te), Y is -OR m or -OC(=O)R n and said 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, Said n, m, l and k are each independently an integer from 1 to 20.

[0065] More specifically, it can include the step of applying an appropriate amount of the above-mentioned composition for edge bead removal of the metal-containing resist along the edge of the substrate while rotating (spin) the substrate at an appropriate speed (for example, 500 rpm or more).

[0066] Next, a first heat treatment step of heating the substrate on which the photoresist film is formed is performed. The first heat treatment step can be performed at a temperature of about 80°C to about 120°C. In this process, the solvent is evaporated, and the photoresist film can be more firmly adhered to the substrate.

[0067] Next, the photoresist film is selectively exposed.

[0068] As an example, examples of light that can be used in the exposure process include not only actinic irradiation rays but also light having a short wavelength such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), etc., and light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc.

[0069] More specifically, the exposure light according to one embodiment can be short-wavelength light having a wavelength range of 5 nm to 150 nm, and can be light having a high energy wavelength such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc.

[0070] At the stage of forming the photoresist pattern, a negative pattern can be formed.

[0071] In the photoresist film, the exposed region becomes different in solubility from the unexposed region of the photoresist film by forming a polymer through a crosslinking reaction such as condensation between organometallic compounds.

[0072] Next, a second heat treatment step is performed on the substrate. The second heat treatment step can be performed at a temperature of about 90°C to about 200°C. By performing the second heat treatment step, the exposed region of the photoresist film becomes difficult to dissolve in the developer.

[0073] Specifically, after dissolving the photoresist film corresponding to the unexposed region using an organic solvent such as 2-heptanone and then removing it, the photoresist pattern corresponding to the negative tone image can be completed.

[0074] As an example of the organic solvent contained in the developer composition used in the pattern formation method according to one embodiment, ketones such as methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, alcohols such as 4-methyl-2-propanol, 1-butanol, isopropanol, 1-propanol, methanol, esters such as propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate, n-butyl acetate, butyrolactone, aromatic compounds such as benzene, xylene, toluene, or combinations thereof can be mentioned.

[0075] As described above, the photoresist pattern formed by exposure not only with light having wavelengths such as i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), but also with light having high energy such as EUV (Extreme UltraViolet; wavelength 13.5 nm), E-Beam (electron beam), etc. can have a width of 5 nm to 100 nm. As an example, the photoresist pattern can be formed with a width of 5 nm to 90 nm, 5 nm to 80 nm, 5 nm to 70 nm, 5 nm to 60 nm, 5 nm to 50 nm, 5 nm to 40 nm, 5 nm to 30 nm, 5 nm to 20 nm.

[0076] On the other hand, the photoresist pattern can have 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 a pitch having a line width roughness of about 10 nm or less, about 5 nm or less, about 3 nm or less, about 2 nm or less.

[0077] Another pattern formation method according to one embodiment includes the steps of applying a metal-containing resist composition on a substrate, removing the edge bead of the metal-containing resist, heat-treating to dry and heat to form a metal-containing resist film on the substrate, exposing the metal-containing photoresist film, and developing using the above-described developer composition for the metal-containing resist.

[0078] The step of applying the metal-containing resist composition on the substrate is as described above.

[0079] The edge bead removal step of the metal-containing resist can be carried out by applying an appropriate amount while rotating the substrate (spin) at an appropriate speed (for example, 500 rpm or more) along the edge of the substrate with a generally known organic solvent or composition for edge bead removal.

[0080] The heat treatment step of drying and heating to form a metal-containing resist film on the substrate is as described above.

[0081] The step of exposing the metal-containing photoresist film is as described above.

[0082] By dissolving the photoresist film corresponding to the unexposed area using the above-mentioned developer composition of the metal-containing resist and then removing it, the photoresist pattern corresponding to the negative tone image can be completed.

[0083] Specific examples of the metal compound contained in the metal-containing resist composition are as described above.

[0084] Next, a method of developing to form a pattern will be specifically described with reference to the drawings.

[0085] FIGS. 2 to 4 are cross-sectional views shown in the order of steps for explaining the pattern formation method.

[0086] Referring to FIG. 2, the exposed photoresist film is developed to form a photoresist pattern 130P.

[0087] In an exemplary embodiment, the exposed photoresist film can be developed to remove the unexposed area of the photoresist film and form a photoresist pattern 130P consisting of the exposed area of the photoresist film. The photoresist pattern 130P can include a plurality of openings OP.

[0088] In an exemplary embodiment, the development of the photoresist film can be performed in an NTD (negative-tone development) process. At this time, as the developer composition, a metal-containing photoresist developer composition according to one embodiment can be used.

[0089] Referring to FIG. 3, the feature layer 110 is processed using the photoresist pattern 130P from the result of FIG. 2.

[0090] For example, in order to process the feature layer 110, various processes can be performed, such as a process of etching the feature layer 110 exposed through the opening OP of the photoresist pattern 130P, a process of implanting impurity ions into the feature layer 110, a process of forming an additional film on the feature layer 110 through the opening OP, and a process of deforming a part of the feature layer 110 through the opening OP. FIG. 3 exemplifies a process of etching the feature layer 110 exposed through the opening OP to form a feature pattern 110P as an exemplary process for processing the feature layer 110.

[0091] Referring to FIG. 4, the photoresist pattern 130P remaining on the feature pattern 110P is removed from the result of FIG. 3. Ashing and strip processes can be used to remove the photoresist pattern 130P.

[0092] Another pattern formation method according to another embodiment includes a step of applying a metal-containing resist composition on a substrate, a step of applying a composition for removing edge beads of the aforementioned metal-containing resist along the edge of the substrate, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, a step of exposing the metal-containing photoresist film, and a step of developing using the aforementioned developer composition of the metal-containing resist.

[0093] The specific methods for each stage are as described above. By simultaneously using the composition for removing edge beads of the metal-containing resist or the developer composition of the metal-containing resist according to the present invention in the edge bead removal stage and the development stage, the removal effect of edge beads and the solubility of the unexposed area are effectively improved, so as to meet the processing and patterning requirements of smaller features, and realize excellent contrast characteristics, excellent sensitivity, and reduced line edge roughness (LER).

Example

[0094] Hereinafter, the present invention will be described in more detail through examples related to the production of the composition for removing edge beads of the above-mentioned metal-containing resist and the developer composition of the metal-containing resist. However, the technical features of the present invention are not limited by the following examples.

[0095] Production of Composition for Removing Edge Beads / Developer Composition of Metal-Containing Resist Example 1 Glutaric acid and Propionic acid were mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in the composition shown in Table 1, and then shaken at room temperature (25°C) until completely dissolved. Then, it was passed through a UPE material filter with a pore size of 0.01 μm to obtain the final composition.

[0096] Examples 2 to 7 and Comparative Examples 1 to 5 Compositions were obtained in the same manner as in Example 1 except that the compositions described in Table 1 below were changed.

[0097]

Table 1

[0098] Production of Metal-Containing Photoresist Composition A metal-containing compound having a structural unit of the following chemical formula C was dissolved in propylene-glycol-methyl-ether-acetate (PGMEA) at a concentration of 3 wt%, and then filtered through a 0.01 μm UPE filter to produce a photoresist composition.

[0099]

Chemical formula

[0100] Evaluation 1: Evaluation of Sn residue 1.0 mL of the photoresist composition according to the above production example was introduced onto an 8-inch silicon wafer, allowed to stand for 20 seconds, and then spin-coated at a speed of 1,500 rpm for 30 seconds. 6.5 mL of the developer composition described in Table 1 was introduced onto the wafer on which the resist film was formed, allowed to stand for 20 seconds, and then spin-dried at a speed of 2,000 rpm for 30 seconds. The steps of introducing the composition, allowing to stand, and spin-drying were repeated 3 times. Then, it was baked at 150 °C for 60 seconds, and the Sn content was confirmed through VPD ICP-MS analysis.

[0101] Evaluation 2: Evaluation over time at room temperature After storing the developer compositions described in Table 1 at room temperature for 3 months each, the residual Sn content was analyzed through VPD ICP-MS analysis. Also, the total amount of carboxylic acid compounds before and after storage (for example, the total content of multi-carboxylic acid and mono-carboxylic acid) was confirmed through GC analysis, and the water content before and after storage was confirmed through Karl-fisher measurement.

[0102] An aging evaluation was performed based on the ratio of the content after 3 months to the content before storage.

[0103]

Table 2

[0104] Referring to Table 2, when applying the metal-containing photoresist developer composition according to the examples, compared with the case of applying the metal-containing photoresist developer composition according to the comparative examples, there are no changes over time in the residual Sn content, the total amount of carboxylic acid compounds, and the moisture content. Therefore, it can be confirmed that it exhibits stable and excellent development performance and maintains the development performance for a long time. Such characteristics can reduce the metal-based contamination inherent in the metal-containing photoresist during process application, enabling the formation of finer patterns and excellent exposure characteristics (sensitivity, CD margin, LWR / LER).

[0105] The specific embodiments of the present invention have been described and illustrated above. However, it is obvious to those with ordinary knowledge in the relevant technical field that the present invention is not limited to the described embodiments and can be variously modified and deformed without departing from the spirit and scope of the present invention. Therefore, such modified or deformed examples should not be individually understood from the technical idea or perspective of the present invention, and it can be said that the deformed embodiments belong to the scope of the claims of the present invention.

Explanation of Reference Signs

[0106] 1... Substrate support part, 2... Injection nozzle, 10... Photoresist solution, 12... Edge bead, 100... Substrate, OP... Opening, 110... Feature layer, 110P... Feature pattern, 130P... Photoresist pattern.

Claims

1. A C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups; A mono-carboxylic acid compound; and An organic solvent, A composition for removing edge beads of a metal-containing resist or a developer composition for a metal-containing resist.

2. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups: The mono-carboxylic acid compound is contained in a weight ratio of 1:0.01 to 1:

2. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1.

3. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups is acyclic. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1.

4. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups is represented by the following Chemical Formula 1. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1. 【Chemical 1】 (In the Chemical Formula 1, L １ is C2-C20 alkylene substituted with at least one of substituted or unsubstituted C3-C20 alkylene, substituted or unsubstituted C3-C20 alkenylene, substituted or unsubstituted C3-C20 alkynylene, C1-C10 aliphatic hydrocarbon group and C6-C12 aromatic hydrocarbon group, C2-C20 alkenylene substituted with at least one of C1-C10 aliphatic hydrocarbon group and C6-C12 aromatic hydrocarbon group, C3-C20 alkynylene substituted with at least one of C1-C10 aliphatic hydrocarbon group and C6-C12 aromatic hydrocarbon group, or a combination thereof, R １ is an amine group, an amide group, a halogen, a hydroxy group, or a carboxyl group, m1 is an integer of 0 or more.)

5. Said L １ is a composition for removing edge beads of a metal-containing resist or a developer composition of a metal-containing resist, which is substituted or unsubstituted propylene, substituted or unsubstituted butylene, substituted or unsubstituted pentylene, substituted or unsubstituted hexylene, substituted or unsubstituted propenylene, substituted or unsubstituted butenylene, substituted or unsubstituted pentenylene, substituted or unsubstituted hexenylene, ethylene substituted with a C1-C10 alkyl group, or a combination thereof, as described in claim 4.

6. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups is one selected from the compounds listed in the following Group 1. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1. 【Chemical formula 2】

7. The mono-carboxylic acid compound is one selected from the compounds listed in the following Group 2. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1. 【Chemical 3】

8. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups and the mono-carboxylic acid compound are contained in an amount of 0.1 to 30% by weight based on the total weight of the composition. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1.

9. The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups and the mono-carboxylic acid compound are contained in an amount of 0.1 to 25% by weight based on the total weight of the composition. The composition for removing edge beads of a metal-containing resist or the developer composition for a metal-containing resist according to Claim 1.

10. Applying a metal-containing resist composition onto a substrate; Edge bead removal step of the metal-containing resist, applying a composition for removing edge beads of the metal-containing resist along the edge of the substrate; Heat treatment step of drying and heating to form a metal-containing photoresist film on the substrate; Exposing the metal-containing photoresist film; and Developing using a developer composition of the metal-containing resist, including The pattern forming method according to claim 1, wherein at least one of the composition for removing edge beads of the metal-containing resist and the developer composition of the metal-containing resist is the composition according to any one of claims 1 to 9.

11. The pattern forming method according to claim 10, wherein the metal compound contained in the metal-containing resist composition contains at least one of an organic oxy group and an organic carbonyloxy group.

12. The pattern forming method according to claim 10, wherein the metal compound contained in the metal-containing resist composition is represented by the following Chemical Formula 2. 【Chemical Formula 4】 (In Chemical Formula 2, R ２ is selected from 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 a substituted or unsubstituted C6-C30 arylalkyl group, R ３ ~R ５ each independently represents 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 arylalkyl group, alkoxo and aryloxo (-OR ａ , where R ａ represents 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 (-O(CO)R ｂ , R ｂ represents 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 alkylamide or dialkylamide (-NR ｃ R ｄ , where R ｃ and R ｄ each independently represents 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 amidato (-NR ｅ (COR ｆ ), where R ｅ and R ｆ is, independently of each other, 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), amidinato (—NR ｇ C(NR ｈ )R ｉ , where R ｇ , R ｈ and R ｉ are, independently of each other, 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), alkylthio and arylthio (—SR ｊ , 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 thiocarboxyl group (—S(CO)R ｋ , 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 ３ ~R ５ At least one of which is alkoxo and aryloxo (-OR ａ、 where 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 (-O(CO)R ｂ where 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 alkylamide or dialkylamide (-NR ｃ R ｄ where R ｃ and R ｄ are each independently 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 amidato (-NR ｅ (COR ｆ where R ｅ and R ｆ are each independently 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 amidinato (-NR ｇ C(NR ｈ )R ｉ where R ｇ R ｈ and R ｉ is, independently of one another, 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), alkylthio and arylthio (-SR ｊ , 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 thiocarboxyl group (-S(CO)R ｋ , R ｋ is selected from 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).)

13. The composition for a semiconductor photoresist according to claim 10, wherein the metal compound contained in the metal-containing resist composition is represented by the following Chemical Formula 3 or Chemical Formula 4: 【Chemical Formula 5】 In Chemical Formula 3, R ６ is a C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; [Chemical Formula 6] 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 aliphatic unsaturated organic group containing one or more double bonds or triple bonds, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C4-C30 heteroaryl group, a carbonyl group, an ethylene oxide group, a propylene oxide group, or a combination thereof, X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ and Said 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, n, m, l, and k are each independently an integer from 1 to 20.

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