A composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists, and a pattern formation method 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 from metal-containing resists or a developer composition for metal-containing resists, and a pattern formation method using the same. [Background technology]

[0002] Recently, the semiconductor industry has seen a continuous reduction in critical dimensions, and this reduction in dimensions has led to a demand for new types of high-performance photoresist materials and patterning methods to meet the requirements for processing and patterning increasingly smaller features.

[0003] Furthermore, the recent dramatic development of the semiconductor industry has created a demand for faster operating speeds and larger storage capacities in semiconductor devices. In line with these demands, process technologies that improve the integration density, reliability, and response speed of semiconductor devices are being developed. In particular, it is important to precisely control / implant impurities into the working regions of the silicon substrate so that these regions are interconnected to form elements and ultra-high-density integrated circuits, which can be achieved through the photolithography process. In other words, it has become important to consider the integration of the photolithography process, which involves coating a substrate with photoresist, selectively exposing it with ultraviolet light (including extreme ultraviolet light), electron beams, or X-rays, and then developing it.

[0004] In particular, 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 the back surface of the substrate, which may cause particles or pattern defects in subsequent semiconductor processes such as etching and ion implantation processes. Therefore, a process of stripping and removing the photoresist applied to the edge and the 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, there is a need 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 above 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. <00'00094> A pattern formation method according to another embodiment includes: applying a metal-containing resist composition onto a substrate; an edge bead removal step of applying a composition for removing edge beads of the metal-containing resist along an 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 of the metal-containing resist, At least one of the composition for removing edge beads of the metal-containing resist and the developer composition of the metal-containing resist contains the aforementioned composition.

Advantages of the Invention

[0010] A composition for removing edge beads of a metal-containing resist according to one embodiment can reduce 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 requirements for processing and patterning smaller features.

[0011] A metal-containing developer composition according to another embodiment has improved detergency and stability over time, facilitating the removal of the photoresist region changed after the exposure process and enabling the maintenance of 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] It is a schematic diagram showing a photoresist coating apparatus. [Figure 2] It is a cross-sectional view showing the process sequence for explaining the pattern formation method. [Figure 3] It is a cross-sectional view showing the process sequence for explaining the pattern formation method. [Figure 4] It is a cross-sectional view showing the process sequence for explaining the pattern formation method.

Modes for Carrying Out the Invention

[0013] The embodiments of the present invention will be described in detail below with reference to the attached drawings. However, in order to clarify the gist of this description, explanations of functions or configurations that are already known will be omitted.

[0014] To clearly explain this description, unnecessary explanatory parts have been omitted, and the same or similar components are denoted by the same reference numerals throughout the specification. Furthermore, the dimensions and thicknesses of each component shown in the drawings are arbitrarily shown for the sake of explanation, and this description is not necessarily limited to those shown in the drawings.

[0015] In the drawings, the thicknesses were enlarged to clearly represent multiple layers and regions. Additionally, the thicknesses of some layers and regions were exaggerated in the drawings for ease of explanation. When a layer, film, region, plate, or other part is described as being "on top" of another part, this includes not only cases where it is "directly above" another part, but also cases where another part lies in between.

[0016] In this description, "substituted" means that the hydrogen atom is substituted with deuterium, halogen group, hydroxyl group, thiol group, cyano group, carbonyl group, carboxyl group, amino group, amide group, ester group, substituted or unsubstituted C1-C30 amine group, nitro group, substituted or unsubstituted C1-C40 silyl group, C1-C30 alkyl group, C1-C10 haloalkyl group, C1-C10 alkylsilyl group, C3-C30 cycloalkyl group, C6-C30 aryl group, C1-C20 alkoxy group, or C1-C20 sulfide group. "Unsubstituted" means that the hydrogen atom remains as a hydrogen atom without being substituted by another substituent.

[0017] In this document, "alkyl group" refers to a linear or branched aliphatic hydrocarbon group unless otherwise defined. An alkyl group may be a "saturated alkyl group" that does not contain any double 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 in which the alkyl chain contains 1 to 5 carbon atoms, and is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

[0019] The alkyl groups mentioned above refer to specific examples such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl groups.

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

[0021] In this document, "cycloalkyl group" refers to a monovalent cyclic aliphatic hydrocarbon group unless otherwise defined.

[0022] The aforementioned cycloalkyl group refers to 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, but is not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group.

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

[0025] In this document, unless otherwise defined, "alkenyl group" refers to a linear or branched aliphatic hydrocarbon group containing one or more double bonds, specifically an aliphatic unsaturated alkenyl group.

[0026] In this document, "alkynyl group" refers to a linear or branched aliphatic hydrocarbon group containing one or more triple bonds, and means an aliphatic unsaturated alkynyl group unless otherwise defined.

[0027] In this description, "aryl group" refers to a substituent in which all elements of the cyclic substituent have p-orbitals, and these p-orbitals form a conjugation, and includes monocyclic or fusion-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) active groups.

[0028] In this description, a "heteroaryl group" means an aryl group containing at least one heteroatom selected from the group consisting of N, O, S, P, and Si. Two or more heteroaryl groups may be directly linked through sigma bonds, or, if the heteroaryl group contains two or more rings, the two or more rings may be fused together. If 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 groups may be, but are not limited to, substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted anthracenyl groups, substituted or unsubstituted phenantrenyl groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, substituted or unsubstituted p-terphenyl groups, substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted o-terphenyl groups, substituted or unsubstituted chrysenyl groups, substituted or unsubstituted benzophenantrenyl groups, substituted or unsubstituted triphenylene groups, substituted or unsubstituted perilennyl groups, substituted or unsubstituted fluorenyl groups, substituted or unsubstituted indenyl groups, or combinations thereof.

[0030] More specifically, substituted or unsubstituted C2-C30 heterocyclic groups include substituted or unsubstituted furanyl groups, substituted or unsubstituted thiophenyl groups, substituted or unsubstituted pyrrolyl groups, substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted imidazolyl groups, substituted or unsubstituted triazolyl groups, substituted or unsubstituted oxazolyl groups, substituted or unsubstituted thiazolyl groups, substituted or unsubstituted oxadiazolyl groups, substituted or unsubstituted thiadiazolyl groups, substituted or unsubstituted pyridyl groups, substituted or unsubstituted pyrimidinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, Substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthilidinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzothiadinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenazinyl group, This may include, but is not limited to, substituted or unsubstituted phenothiazinyl groups, substituted or unsubstituted phenoxazinyl groups, substituted or unsubstituted carbazolyl groups, substituted or unsubstituted dibenzofuranyl groups, or substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted benzonaphthofuranyl groups, substituted or unsubstituted benzonaphthothiophenyl groups, substituted or unsubstituted benzofuranofurenyl groups, substituted or unsubstituted benzothiophenefluorenyl groups, or combinations thereof.

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

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

[0033] The substrate support unit 1 rotates in a first direction at a predetermined rotational speed, providing centrifugal force to the substrate W. An injection nozzle 2 is located on the substrate support unit 1, and the injection nozzle 2 is located in an atmospheric area away from the top of the substrate W. During the solution supply stage, it moves to the top of the substrate to spray the photoresist solution 10. As a result, 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 to the periphery of the substrate W by the centrifugal force, and a portion of it moves to the side surface of the substrate and the lower surface of the periphery of the substrate.

[0034] In other words, in the coating process, the photoresist solution 10 is mainly applied by a spin coating method, but a predetermined amount of viscous photoresist solution 10 is supplied to the center of the substrate W and gradually diffuses toward the periphery of the substrate by centrifugal force.

[0035] Therefore, the thickness of the photoresist is formed flat by the rotation speed of the substrate support.

[0036] However, as the solvent evaporates and the viscosity gradually increases, a relatively large amount of photoresist accumulates at the periphery of the substrate due to the action of surface tension, and more seriously, the photoresist accumulates up to the bottom surface of the periphery of the substrate, which is called an edge bead 12.

[0037] The following describes a composition for removing edge beads from metal-containing resists or a developer composition for metal-containing resists according to one embodiment.

[0038] A composition for removing edge beads from metal-containing resists or a developer solution composition for metal-containing resists according to one embodiment of the present invention comprises a C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups; a mono-carboxylic acid compound; and an organic solvent.

[0039] The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups: The mono-carboxylic acid compound may be present in a weight ratio of 1:0.01 to 1:2.

[0040] As an example, the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups:the mono-carboxylic acid compound may be present in weight ratios of 1:0.1-1:2, 1:0.1-1:1.5, 1:0.2-1:1.5, 1:0.3-1:1.5, or 1:0.4-1:1.5.

[0041] By using a mixture of the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups and the mono-carboxylic acid compound, the temporal stability of the composition is improved, and the cleaning power is enhanced, minimizing various contaminating particles generated by metal-containing photoresist on the edges or back surface of the substrate, facilitating the removal of altered photoresist areas after the exposure process, and maintaining removal performance over a long period of time. This enables the realization of excellent exposure characteristics (sensitivity, CD margin, LWR / LER).

[0042] In this specification, the carbon number of C3-C20 aliphatic hydrocarbon compounds substituted with at least two carboxyl groups does not include the carbons contained in the carboxyl groups.

[0043] For example, in the case of a C3 aliphatic hydrocarbon compound substituted with at least two carboxyl groups, it means a structure in which at least two carboxyl groups are substituted on an aliphatic hydrocarbon with three carbon atoms.

[0044] Specifically, the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups may be acyclic.

[0045] For example, the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups can be represented by the following chemical formula 1.

[0046] [ka] In the aforementioned chemical formula 1, L 1 These are substituted or unsubstituted C3-C20 alkylenes, substituted or unsubstituted C3-C20 alkenylenes, substituted or unsubstituted C3-C20 alkylenes, C2-C20 alkylenes substituted with at least one of C1-C10 aliphatic hydrocarbon groups and C6-C12 aromatic hydrocarbon groups, C2-C20 alkenylenes substituted with at least one of C1-C10 aliphatic hydrocarbon groups and C6-C12 aromatic hydrocarbon groups, C3-C20 alkylenes substituted with at least one of C1-C10 aliphatic hydrocarbon groups and C6-C12 aromatic hydrocarbon groups, or combinations thereof. R 1 These are amine groups, amide groups, halogens, hydroxyl groups, or carboxyl groups. m1 is a non-negative integer.

[0047] The upper limit of m1 is L 1 m1 can be the maximum value that can be connected to, but m1 can be within the range of 1 to 10, 1 to 8, 1 to 6, or 1 to 3, within the range of the above maximum value or less.

[0048] In one embodiment, L 1 This may be 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 C1-C10 alkyl groups, or a combination thereof.

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

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

[0051] [ka] The C3-C20 aliphatic hydrocarbon compounds and mono-carboxylic acid compounds substituted with at least two carboxyl groups may be present in an amount of 0.1-30% by weight based on the total weight of the composition.

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

[0053] The metal-containing resist edge bead removal composition according to the present invention may be particularly effective in removing metal-containing resists, and more specifically, undesirable metal residues, such as tin-based metal residues.

[0054] Furthermore, the metal-containing resist developer composition according to the present invention minimizes defects present in the metal-containing photoresist film after the exposure process, enabling easy development and thereby achieving excellent pattern characteristics.

[0055] Furthermore, it can also achieve superior sensitivity and reduced line edge roughness (LER).

[0056] If other additives described later are included, the organic solvent may be included in the amount remaining after deducting the components that are included.

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

[0058] On the other hand, according to another embodiment, a pattern forming method may be provided that includes the step of removing edge beads using the aforementioned metal-containing resist edge bead removal composition. As an example, the manufactured pattern may be a photoresist pattern. More specifically, it may be a negative-type photoresist pattern.

[0059] A pattern formation method according to one embodiment includes the steps of: applying a metal-containing resist composition onto a substrate; applying the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing.

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

[0061] For example, the metal compound contained in the metal-containing resist composition may be represented by the following chemical formula 2.

[0062] [ka] In the aforementioned chemical formula 2, R 2 These are selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C6-C30 arylalkyl groups. R3 ~R 5 is, independently, 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 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 fEach of these is 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 C2C20 alkynyl group, a substituted or unsubstituted C6-C30 aryl group, or a combination thereof), amidinate (-NR) g C(NR h )R i , here, R g , R h and R i Each of these is 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), alkylthio and arylthio (-SR j , here, R j (which 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 (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R 3 ~R 5 At least one of them is an alcoxo and an aryloxo (-OR a , here, R a(which are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R b , R b (which 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), alkylamide or dialkylamide (-NR c R d , here, R c and R d Each of these is 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), amidato (-NR e (COR f ), here, R e and R f Each of these is 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), amidinate (-NR) g C(NR h )R i , here, R g , R h and R iEach of these is 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), alkylthio and arylthio (-SR j , here, R j (which 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 (The group is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof.)

[0063] Furthermore, the metal compound contained in the metal-containing resist composition may be represented by the following chemical formula 3 or chemical formula 4.

[0064] [ka] In the aforementioned chemical formula 3, R 6 This is the C1-C31 hydrocarbyl group, where 0 <z≦2であり、0<(z+x)≦4であり; [ka] In the aforementioned chemical formula 4, R 7These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te). Y is -OR m Or -OC(=O)R n And, The aforementioned R m These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R n This includes hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The aforementioned n, m, l, and k are each independent integers between 1 and 20.

[0065] More specifically, the process may include a step of applying an appropriate amount of the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate while rotating (spinning) the substrate at an appropriate speed (e.g., 500 rpm or more).

[0066] Next, a first heat treatment step is performed in which the substrate on which the photoresist film is formed is heated. The first heat treatment step can be performed at a temperature of about 80°C to about 120°C, during which the solvent is evaporated and the photoresist film can be adhered more firmly 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 short-wavelength light such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm) as activation irradiation lines, but also high-energy wavelength light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam).

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

[0070] During the process of forming the photoresist pattern, a negative-type pattern can be formed.

[0071] In a photoresist film, the exposed regions form polymers through crosslinking reactions such as condensation between organometallic compounds, resulting in different solubility levels from the unexposed regions of the photoresist film.

[0072] Next, a second heat treatment step is performed on the substrate. This second heat treatment step can be carried out at a temperature of approximately 90°C to approximately 200°C. By performing this second heat treatment step, the exposed area of ​​the photoresist film becomes difficult to dissolve in the developer solution.

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

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

[0075] As mentioned above, photoresist patterns formed by exposure with light having wavelengths such as i-line (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), as well as high-energy light such as EUV (Extreme UltraViolet; wavelength 13.5nm) and E-Beam (electron beam), can have a width of 5nm to 100nm in thickness. For example, the photoresist patterns can be formed with widths of 5nm to 90nm, 5nm to 80nm, 5nm to 70nm, 5nm to 60nm, 5nm to 50nm, 5nm to 40nm, 5nm to 30nm, and 5nm to 20nm in thickness.

[0076] On the other hand, the photoresist pattern may have a half-pitch of approximately 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 approximately 10 nm or less, approximately 5 nm or less, approximately 3 nm or less, or approximately 2 nm or less.

[0077] Another embodiment of the pattern formation method includes the steps of applying a metal-containing resist composition onto a substrate, removing edge beads of the metal-containing resist, a heat treatment step of drying and heating to form a metal-containing resist film on the substrate, an exposure step of the metal-containing photoresist film, and developing using the aforementioned metal-containing resist developer composition.

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

[0079] The edge bead removal step for metal-containing resists can be performed by applying an appropriate amount of a commonly known edge bead removal organic solvent or composition along the edge of the substrate while rotating (spinning) the substrate at an appropriate speed (e.g., 500 rpm or more).

[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 using the aforementioned metal-containing resist developer composition to dissolve and then remove the photoresist film corresponding to the unexposed areas, a photoresist pattern corresponding to the negative tone image can be completed.

[0083] Specific examples of metal compounds included in the aforementioned metal-containing resist composition are as described above.

[0084] Next, we will explain in detail how to develop and form patterns, using a drawing as an example.

[0085] Figures 2 to 4 are cross-sectional views illustrating the pattern formation method in order of the process steps.

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

[0087] In an exemplary embodiment, the exposed photoresist film can be developed to remove the unexposed regions of the photoresist film, thereby forming a photoresist pattern 130P consisting of the exposed regions of the photoresist film. The photoresist pattern 130P may include a plurality of apertures OP.

[0088] In the exemplary embodiment, the photoresist film can be developed using a negative-tone development (NTD) process. In this case, a metal-containing photoresist developer composition according to one embodiment can be used as the developer composition.

[0089] Referring to Figure 3, the feature layer 110 is fabricated using the photoresist pattern 130P from the result in Figure 2.

[0090] For example, various processes can be performed to process the feature layer 110, such as etching the feature layer 110 exposed through the opening 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 opening OP, and deforming a part of the feature layer 110 through the opening OP. Figure 3 illustrates an example of a process for processing the feature layer 110, which involves etching the feature layer 110 exposed through the opening OP to form the feature pattern 110P.

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

[0092] Another embodiment of the pattern formation method includes the steps of: applying a metal-containing resist composition onto a substrate; applying the aforementioned metal-containing resist edge bead removal composition along the edge of the substrate; a heat treatment step of drying and heating to form a metal-containing resist film on the substrate; exposing the metal-containing photoresist film; and developing it using the aforementioned metal-containing resist developer composition.

[0093] The specific methods for each stage are as described above. By simultaneously utilizing the edge bead removal composition for metal-containing resists or the developer solution composition for metal-containing resists according to the present invention in the edge bead removal stage and the development stage, the edge bead removal effect and the solubility of unexposed areas are effectively improved, thereby meeting the requirements for processing and patterning smaller features and achieving excellent contrast characteristics, superior sensitivity, and reduced line edge roughness (LER). [Examples]

[0094] The present invention will be described in more detail below through examples relating to the production of the aforementioned metal-containing resist edge bead removal composition and metal-containing resist developer composition. However, the technical features of the present invention are not limited by the following examples.

[0095] Manufacturing of compositions for removing edge beads from metal-containing resists / developer compositions Example 1 Glutaric acid and propionic acid are mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent in the compositions shown in Table 1, and then shaken at room temperature (25°C) to completely dissolve. The mixture is then passed through a UPE filter with a pore size of 0.01 μm to obtain the final composition.

[0096] Examples 2-7 and Comparative Examples 1-5 A composition is obtained in the same manner as in Example 1, except that the composition is changed to that shown in Table 1 below.

[0097] [Table 1]

[0098] Manufacturing of metal-containing photoresist compositions A metal-containing compound having the structural unit of chemical formula C shown below 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] [ka]

[0100] Evaluation 1: Evaluation of Sn residue 1.0 mL of the photoresist composition according to the above manufacturing example is placed on an 8-inch silicon wafer and left for 20 seconds, then spin-coated at a speed of 1,500 rpm for 30 seconds. 6.5 mL of each of the developer compositions listed in Table 1 is placed on the wafer with the resist film formed, left for 20 seconds, then spin-dried at a speed of 2,000 rpm for 30 seconds. The process of adding the composition, leaving it to stand, and spin-drying is repeated three times. After that, the wafers are baked at 150°C for 60 seconds, and the Sn content is confirmed by VPD ICP-MS analysis.

[0101] Evaluation 2: Evaluation at room temperature The developer compositions listed in Table 1 were stored at room temperature for 3 months, and the residual Sn content was analyzed by VPD ICP-MS analysis. In addition, the total amount of carboxylic acid compounds (e.g., the total content of multi-carboxylic acids and mono-carboxylic acids) before and after storage was confirmed by GC analysis, and the moisture content before and after storage was confirmed by Karl-Fisher measurement.

[0102] Time-course evaluation was performed by comparing the content after 3 months with the content before storage.

[0103] [Table 2]

[0104] Referring to Table 2, it can be confirmed that when the metal-containing photoresist developer composition according to the example is applied, there is no change over time in residual Sn content, total amount of carboxylic acid compounds, and water content compared to when the metal-containing photoresist developer composition according to the comparative example is applied, thus exhibiting stable and excellent development performance and maintaining development performance for a long period of time. Such characteristics allow for the reduction of metal base contamination inherent in the metal-containing photoresist during process application, enabling the formation of even finer patterns and excellent exposure characteristics (sensitivity, CD margin, LWR / LER).

[0105] Although specific embodiments of the present invention have been described and illustrated above, it will be obvious to those ordinary skill in the art that the present invention is not limited to the described embodiments and can be modified and transformed in various ways without departing from the spirit and scope of the invention. Therefore, such modifications or variations should not be understood individually from the technical spirit or viewpoint of the invention, and the modified embodiments can be said to fall within the scope of the claims of the present invention. [Explanation of symbols]

[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. C3-C20 aliphatic hydrocarbon compounds substituted with at least two carboxyl groups (where C3-C20 refers to the number of carbon atoms in the aliphatic hydrocarbon portion excluding the carbon atoms contained in the carboxyl groups); A monocarboxylic acid compound selected from the compounds listed in Group 2 below; and Contains organic solvents, The C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups is represented by the following chemical formula 1, The C3-C20 aliphatic hydrocarbon compounds and mono-carboxylic acid compounds substituted with at least two carboxyl groups are present in an amount of 0.1 to 30% by weight based on the total weight of the composition. A composition for removing edge beads from metal-containing resists, or a developer composition for metal-containing resists. 【Chemistry 1】 (In the above chemical formula 1, L1 is a substituted or unsubstituted C3-C20 alkylene, a substituted or unsubstituted C3-C20 alkenylene, a substituted or unsubstituted C3-C20 alkylene, 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 alkylene substituted with at least one of a C1-C10 aliphatic hydrocarbon group and a C6-C12 aromatic hydrocarbon group, or a combination thereof. R1 is an amine group, amide group, halogen, hydroxyl group, or carboxyl group. m1 is a non-negative integer. 【Chemistry 2】

2. The composition for removing edge beads from a metal-containing resist or the developer composition for a metal-containing resist according to claim 1, wherein the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups and the mono-carboxylic acid compound are present in a weight ratio of 1:0.01 to 1:

2.

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

4. Said L １ The composition for removing edge beads from metal-containing resists or the developer composition for metal-containing resists according to claim 1, wherein 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.

5. The metal-containing resist edge bead removal composition or metal-containing resist developer composition according to claim 1, wherein the C3-C20 aliphatic hydrocarbon compound substituted with at least two carboxyl groups is selected from the compounds listed in Group 1 below. 【Transformation 3】

6. The metal-containing resist edge bead removal composition or metal-containing resist developer composition according to claim 1, wherein 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.

7. The step of applying a metal-containing resist composition onto a substrate; A metal-containing resist edge bead removal step, in which a metal-containing resist edge bead removal composition is applied along the edge of the substrate; A heat treatment step in which a metal-containing photoresist film is formed on the substrate by drying and heating; The step of exposing the metal-containing photoresist film; and The process includes developing the metal-containing resist using a developer composition, A pattern forming method wherein at least one of the metal-containing resist edge bead removal composition and the metal-containing resist developer composition is the composition described in any one of claims 1 to 6.

8. The pattern forming method according to claim 7, wherein the metal compound contained in the metal-containing resist composition comprises at least one of an organic oxy group and an organic carbonyl oxy group.

9. The pattern forming method according to claim 7, wherein the metal compound contained in the metal-containing resist composition is represented by the following chemical formula 2. 【Chemistry 4】 (In the above chemical formula 2, R ２ These are selected from substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C6-C30 arylalkyl groups. R ３ ~R ５ are each independently 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 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 , 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-C2o 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 Each of these is 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), amidinate (amidinato) (-NR ｇ C (NR ｈ ) R ｉ Here, R ｇ , R ｈ and R ｉ Each of these is 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), alkylthio and arylthio (-SR ｊ Here, R ｊ (which 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 (These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof.) R ３ ~R ５ At least one of them is an alcoxo and an aryloxo (-OR ａ、 Here, R ａ (These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof), carboxyl groups (-O(CO)R ｂ , R ｂ (-NR) ｃ R ｄ Here, R ｃ and R ｄ Each of these is 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), amidate (amidato) (-NR ｅ (COR ｆ ), here, R ｅ and R ｆ Each of these is 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), amidinate (amidinato) (-NR ｇ C (NR ｈ ) R ｉ Here, R ｇ , R ｈ and R ｉ Each of these is 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), alkylthio and arylthio (-SR ｊ Here, R ｊ (which 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 (The group is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or a combination thereof.)

10. The metal compound contained in the metal-containing resist composition is represented by the following chemical formula 3 or chemical formula 4, as described in the pattern forming method of claim 7: 【Transformation 5】 In the aforementioned chemical formula 3, R ６ These are the C1-C31 hydrocarbyl group, where 0 < z ≤ 2 and 0 < (z + x) ≤ 4; 【Transformation 6】 In the aforementioned chemical formula 4, R ７ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 aliphatic unsaturated organic groups containing one or more double or triple bonds, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C4-C30 heteroaryl groups, carbonyl groups, ethylene oxide groups, propylene oxide groups, or combinations thereof. X is sulfur (S), selenium (Se), or tellurium (Te), Y is -OR ｍ or -OC(=O)R ｎ And, The aforementioned R ｍ These are substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. R ｎ These are hydrogen, substituted or unsubstituted C1-C20 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C2-C20 alkenyl groups, substituted or unsubstituted C2-C20 alkynyl groups, substituted or unsubstituted C6-C30 aryl groups, or combinations thereof. The aforementioned n, m, l, and k are each independent integers between 1 and 20.

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