Resist composition and pattern forming method using same

Abstract

Disclosed are a resist composition and a pattern forming method using the same. The resist composition may include an organometallic compound represented by any one of Formulae 1-1 to 1-4, an additive represented by Formula 2, and a solvent. The solvent may include a non-polar solvent, a polar aprotic solvent, or a combination thereof. For the description of M11, L11 to L14, a11 to a14, R11 to R14, b11 to b14, Y11 to Y13, X11 to X13, Y21, Y22, L21 and a21 in Formulae 1-1 to 1-4 and 2, the description is referred to as the description of M11, L11 to L14, a11 to a14, R11 to R14, b11 to b14, Y11 to Y13, X11 to X13, Y21, Y22, L21 and a21. Lt; formula 2gt;

Description

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Application No. 10-2024-0061263, filed on May 9, 2024, with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This disclosure relates to resist compositions and methods for patterning using the same. Background Technology

[0004] In semiconductor manufacturing, photoresists whose physical properties change in response to light are being used to form intricate patterns. Among these photoresists, chemically amplified photoresists are widely used. In the case of chemically amplified photoresists, an acid formed through a reaction between light and a photoacid-generating agent reacts with the base resin to alter the solubility of the base resin in the developer, thereby enabling patterning.

[0005] However, in the case of chemically amplified resists, the diffusion of the formed acid into unexposed areas can lead to poor pattern uniformity and increased surface roughness. Furthermore, with increasingly miniaturized semiconductor processes, acid diffusion is difficult to control, thus necessitating the development of novel resists.

[0006] Recently, in an effort to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change upon exposure to light. However, the required exposure dose remains high. Summary of the Invention

[0007] A photoresist composition and a method of patterning therewith are provided, the photoresist composition having improved storage stability, its properties not changing even with low doses of exposure, and providing patterned patterns with improved resolution.

[0008] Other aspects will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the embodiments presented in this disclosure.

[0009] According to embodiments, the resist composition may include an organometallic compound represented by any one of formulas 1-1 to 1-4, an additive represented by formula 2, and a solvent, wherein the solvent may include a nonpolar solvent, a polar aprotic solvent, or a combination thereof.

[0010]

[0011] Among them, in equations 1-1 to 1-4 and 2,

[0012] M 11It can be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po);

[0013] L 11 To L 14 Each can be a straight-chain, branched, or cyclic C1-C bond, independently of a single bond or substituted or unsubstituted, optionally including heteroatoms. 30 Divalent hydrocarbon groups,

[0014] a11 to a14 can each be independently selected from integers from 1 to 4.

[0015] R 11 To R 14 Each is independently either substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C7-C 30 arylalkyl, substituted or unsubstituted C1-C 30 heteroaryl, or substituted or unsubstituted C2-C 30 heteroarylalkyl,

[0016] R 11 To R 14 Two adjacent elements may optionally bond (join) with each other to form a ring (e.g., a fused ring).

[0017] b11 to b14 can each be independently selected from integers from 1 to 4.

[0018] Y 11 To Y 13 Each can be independently O, OC (=O), S, SC (=O), NX 14 , or NX 14 C(=O),

[0019] X 11 To X 14 Each can independently be hydrogen, deuterium, or a straight-chain, branched, or cyclic C1-C, optionally substituted or unsubstituted, including heteroatoms. 30 Monovalent hydrocarbon groups,

[0020] Y 21 and Y22 Each can be independently substituted or unsubstituted, including straight-chain, branched, or cyclic C1-C atoms, with at least one heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus atoms as heteroatoms. 30 Monovalent hydrocarbon groups,

[0021] L 21 It can be a single bond, a double bond, or a straight-chain, branched, or cyclic C1-C structure, optionally including heteroatoms, with or without substitution. 30 Divalent hydrocarbon groups,

[0022] a21 can be any integer from 1 to 4.

[0023] Y 21 Y 22 and L 21 Two adjacent elements may optionally be bonded to each other to form a fused ring.

[0024] According to embodiments of the present disclosure, a method for forming a pattern may include: applying the resist composition to form a resist film, exposing at least a portion of the resist film to high-energy radiation to provide an exposed resist film, and developing the exposed resist film using a developer. Attached Figure Description

[0025] The above and other aspects, features, and advantages of some embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, wherein:

[0026] Figure 1 A flowchart illustrating the method for forming a pattern according to the embodiment;

[0027] Figures 2A to 2C A side cross-sectional view showing the method for forming a pattern according to an embodiment;

[0028] Figures 3A to 3E A side cross-sectional view showing the method for forming a patterned structure according to an embodiment;

[0029] Figures 4A to 4E A side cross-sectional view showing the method for forming a semiconductor device according to an embodiment;

[0030] Figure 5A A graph showing the change in film thickness after development according to dosage in Examples 1-1;

[0031] Figure 5B A graph showing the change in film thickness after development according to dosage in Comparative Example 1-1; and

[0032] Figures 6A to 6E The graphs show the changes in film thickness after development according to dosage in Examples 2-1 to 2-5, respectively. Detailed Implementation

[0033] The embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings, wherein similar reference numerals always refer to similar elements. In this respect, the embodiments may take different forms and should not be construed as limited to the description set forth herein. Therefore, embodiments are described below only by reference to the accompanying drawings to illustrate aspects. As used herein, the term “and / or” includes any and all combinations of one or more of the associated enumerated items. Expressions such as “at least one of” modify the entire list of elements and not individual elements of that list when preceding or following it. For example, “at least one of A, B, and C” and similar language (e.g., “at least one of A, B, and C”) can be interpreted as only A, only B, only C, or any combination of two or more of A, B, and C, such as ABC, AB, BC, and AC.

[0034] When the terms “about” or “substantially” are used in this specification with respect to numerical values, it is intended that the relevant numerical values ​​include manufacturing or operational tolerances (e.g., ±10%) around the stated numerical values. Similarly, when the terms “generally” and “substantially” are used with respect to geometry, it is intended that precision of the geometry is not required, but rather a tolerance for the shape within the scope of this disclosure. Furthermore, regardless of whether a numerical value or shape is modified by “about” or “substantially,” it will be understood that these values ​​and shapes should be interpreted as including manufacturing or operational tolerances (e.g., ±10%) around the stated numerical value or shape. When ranges are described in detail, the ranges include all values ​​therebetween, for example, in increments of 0.1%.

[0035] Because this disclosure allows for various modifications and numerous implementations, specific embodiments will be shown in the accompanying drawings and described in detail in the written description. However, this is not intended to limit this disclosure to a particular mode of practice, and it will be understood that all modifications, equivalents, and alternatives that do not depart from the spirit and scope of this disclosure are included within its scope. In the description of this disclosure, detailed descriptions of known related technologies will be omitted where it is determined that such detailed descriptions would unnecessarily obscure the main points of this disclosure.

[0036] Although the terms “first,” “second,” “third,” etc., may be used in this document to describe various elements, these terms are only used to distinguish one element from another, and therefore the order, type, etc., of the elements are not restricted.

[0037] In this specification, when a portion of a layer, film, region, plate, etc., is described as being "on" or "above" another portion, it may include not only the meaning of "directly above / below / left / right in contact with" but also the meaning of "above / below / left / right in a non-contact manner".

[0038] A singular expression encompasses a plural expression unless it has a distinct meaning in the context. Unless explicitly stated otherwise, terms such as “comprising” and “having” are intended to indicate the presence of features, figures, steps, actions, components, parts, ingredients, materials, or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, figures, steps, actions, components, parts, ingredients, materials, or combinations thereof may be present or added.

[0039] Whenever a range of values ​​is listed, the range includes all values ​​falling within that range, as if explicitly stated, and the range further includes the boundaries of the range. Therefore, the range "X to Y" includes all values ​​between X and Y, and also includes X and Y.

[0040] The term "C" is used in this article. x -C y "C1-C6" refers to cases where the number of carbon atoms constituting the group or substituent is in the range of x to y. For example, the expression "C1-C6" refers to cases where the number of carbon atoms constituting the group or substituent is in the range of 1 to 6, and the expression "C6-C6" refers to cases where the number of carbon atoms constituting the group or substituent is in the range of 1 to 6. 20 "This refers to cases where the number of carbon atoms constituting a group or substituent is in the range of 6 to 20.

[0041] As used herein, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound or a derivative thereof comprising carbon and hydrogen, and specific examples include straight-chain or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); monovalent saturated alicyclic hydrocarbon groups (cycloalkyl) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornel, norbornelmethyl, tricyclodecyl, tetracyclododecyl, etc.). Tetracyclododecylmethyl and dicyclohexylmethyl); monovalent unsaturated aliphatic hydrocarbon groups (alkenyl or ynyl) (e.g., allyl); monovalent unsaturated alicyclic hydrocarbon groups (cycloalkenyl) (e.g., 3-cyclohexenyl); aryl (e.g., phenyl, 1-naphthyl, and 2-naphthyl); arylalkyl (e.g., benzyl and diphenylmethyl); monovalent hydrocarbon groups including heteroatoms (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamylmethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl), or combinations thereof. In addition, some of the hydrogen atoms in these groups may be partially replaced by heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, or halogen atoms, or some of the carbon atoms in these groups may be partially replaced by heteroatoms such as oxygen, sulfur, nitrogen, or phosphorus. Therefore, these groups may include cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulcinolone moiety, carboxylic anhydride moiety, etc.

[0042] As used herein, the term "divalent hydrocarbon group" refers to a divalent residue and means a system in which any hydrogen atom of a monovalent hydrocarbon group is replaced by a binding site with an adjacent atom. Divalent hydrocarbon groups may include, for example, straight-chain or branched alkylene, cycloalkylene, alkenylene, ynylene, cycloalkenylene, arylene, groups in which some of their carbon atoms are replaced by heteroatoms, etc.

[0043] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic monovalent hydrocarbon group, and examples of such groups may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. As used herein, the term "alkylene" refers to a straight-chain or branched saturated aliphatic divalent hydrocarbon group, and examples of such groups may include methylene, ethylene, propylene, butylene, and isobutylene.

[0044] As used herein, the term "haloalkyl" refers to a group in which at least one hydrogen atom of the alkyl group is replaced by a halogen atom, and examples include -CF3. The halogen atom is F, Cl, Br, or I.

[0045] As used in this article, the term "alkoxy" refers to the compound formed by the formula -OA. 101 The monovalent group represents A. 101 It is an alkyl group. Specific examples include methoxy, ethoxy, and isopropoxy groups.

[0046] As used in this article, the term "alkylthio" refers to the group composed of the formula SA. 101 The monovalent group represents A. 101 It is an alkyl group.

[0047] As used herein, the term "haloalkoxy" refers to a group in which one or more hydrogen atoms of the alkoxy group are replaced by halogen atoms, and specific examples include -OCF3, etc.

[0048] As used herein, the term "haloalkylthio" refers to a group in which one or more hydrogen atoms of the alkylthio group are replaced by halogen atoms, and specific examples include -SCF3, etc.

[0049] As used herein, the term "cycloalkyl" refers to a monovalent saturated hydrocarbon cyclic group, and specific examples include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; and bridged cycloalkyl groups such as norcamphenyl and adamantyl. As used herein, the term "cycloalkylene" refers to a divalent saturated hydrocarbon cyclic group, and specific examples include cyclopentylene, cyclohexylene, adamantylene, adamantylmethylene, norcamphenylene, norcamphenylmethylene, tricyclodecylene, tetracyclododecylene, tetracyclododecylmethylene, dicyclohexylmethylene, etc.

[0050] As used in this article, the term "cycloalkoxy" refers to a compound of the formula -OA. 102 The monovalent group represents A. 102 It is a cycloalkyl group. Specific examples include cyclopropoxy and cyclobutoxy.

[0051] As used in this article, the term "cycloalkylthio" refers to the compound formed by the formula -SA 102 The monovalent group represents A. 102 It is a cycloalkyl group.

[0052] As used herein, the term "heterocyclic alkyl" refers to a cycloalkyl group in which some of its carbon atoms are partially substituted with heteroatoms such as oxygen, sulfur, or nitrogen, and heterocyclic alkyl groups may include ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, or carboxylic anhydride moieties. As used herein, the term "heterocyclic alkylene" refers to a group in which some of its carbon atoms are partially substituted with heteroatoms such as oxygen, sulfur, or nitrogen.

[0053] As used in this article, the term "heterocyclic alkoxy" refers to a compound of the formula -OA. 103 The monovalent group represents A. 103 It is a heterocyclic alkyl group.

[0054] As used in this article, the term "heterocyclic alkylthio" refers to a compound of the formula -SA 103 The monovalent group represents A. 103 It is a heterocyclic alkyl group.

[0055] As used herein, the term "alkenyl" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group comprising one or more carbon-carbon double bonds. As used herein, the term "alkenylidene" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon divalent group comprising one or more carbon-carbon double bonds.

[0056] As used herein, the term "cycloalkenyl" refers to a monovalent unsaturated hydrocarbon cyclic group that comprises at least one carbon-carbon double bond and is non-aromatic. As used herein, the term "cycloalkenylene" refers to a divalent unsaturated hydrocarbon cyclic group that comprises at least one carbon-carbon double bond and is non-aromatic.

[0057] As used herein, the term "heterocyclic alkenyl" refers to a cycloalkenyl group in which some of its carbon atoms are partially replaced by heteroatoms such as oxygen, sulfur, or nitrogen. As used herein, the term "hemiecyclic alkenyl" refers to a cycloalkenyl group in which some of its carbon atoms are partially replaced by heteroatoms such as oxygen, sulfur, or nitrogen.

[0058] As used herein, the term "alkynyl" refers to a straight-chain or branched monovalent unsaturated aliphatic hydrocarbon group that includes one or more carbon-carbon triple bonds.

[0059] As used herein, the term "aryl" refers to a monovalent group comprising a carbocyclic aromatic system, and examples include phenyl, naphthyl, anthraceneyl, phenanthryl, pyrene, and... Element. As used herein, the term "arylene" refers to a divalent group including carbocyclic aromatic systems.

[0060] As used in this article, the term "aryloxy group" refers to the group formed by the formula -OA. 104 The monovalent group represents A. 104 It is an aryl group.

[0061] As used in this article, the term "arylthio" refers to the group derived from the formula -SA 104 The monovalent group represents A. 104 It is an aryl group.

[0062] As used herein, the term "heteroaryl" refers to a monovalent group comprising a heterocyclic aromatic system, and examples of such groups include pyridyl, pyrimidinyl, and pyrazinyl. As used herein, the term "hybridaryl" refers to a divalent group comprising a heterocyclic aromatic system.

[0063] As used in this article, the term "heteroaryloxy" refers to a compound derived from the formula -OA. 105 The monovalent group represents A. 105 It is a heteroaryl group.

[0064] As used in this article, the term "heteroaryl thio" refers to a compound of the formula -SA 105 The monovalent group represents A. 105 It is a heteroaryl group.

[0065] As used herein, the term "arylalkyl" refers to a group in which the alkyl group is replaced by a monovalent group having a carbocyclic aromatic system, and specific examples include benzyl, diphenylmethyl, etc.

[0066] As used herein, the term "heteroarylalkyl" refers to a group in which the alkyl group is replaced by a monovalent group having a heterocyclic aromatic system.

[0067] As used herein, the term "heterocyclic group" refers to a monocyclic or polycyclic group having 1 to 60 carbon atoms, including at least one heteroatom, and may include monovalent, divalent, and trivalent groups.

[0068] As used herein, the term "substituent" includes deuterium, halogen atom, cyano, nitro, hydroxyl, thiol group, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C20 heteroaryl, C1-C 20 heteroaryloxy or C1-C 20 heteroaryl thiols;

[0069] Each of the following C1-C is replaced: 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 heteroaryl, C1-C 20 Heteroaryl groups and C1-C 20 Heteroaryl thiols: deuterium, halogen atom, cyano, nitro, hydroxyl, thiol group, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 heteroaryl, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols, or combinations thereof; and

[0070] Its combination.

[0071] In this document, the expression "C1-C" is used when describing any group or substituent. 30 “C2-C” 30 “C3-C” 30 “C6-C” 30 "and "C7-C30 The upper limit C in " 30 It can preferably be changed to C 20 C 14 C 13 C 12 C 11 C 10 C1, C9, C8, or C6, and the expression "C1-C6" is used when describing any group or substituent. 20 “C3-C” 20 " and "C6-C 20 The upper limit C in " 20 It can preferably be changed to C 14 C 13 C 12 C 11 C 10 C1, C9, C8, or C6. For example, C1-C 30 Alkyl groups are preferably C1-C. 20 Alkyl groups, such as C1-C 10 Alkyl or C1-C6 alkyl; C2-C 30 The alkenyl group can preferably be C2-C. 20 alkenyl, C2-C 10 alkenyl, or C2-C6 alkenyl; C3-C 30 The cycloalkyl group may preferably be C3-C 20 cycloalkyl, for example C3-C 10 Cycloalkyl or C3-C8 cycloalkyl; C6-C 30 The aryl group is preferably C6-C. 20 Aryl, for example C6-C 12 Aryl or C6-C 10 Aryl; C7-C 30 The aryl alkyl group is preferably C7-C. 20 Arylalkyl, for example C7-C 14 Arylalkyl, C7-C 12 arylalkyl, or C7-C 10 Arylalkyl; C1-C 30 The heteroaryl group is preferably C1-C. 20 heteroaryl, such as C3-C 10 Heteroaryl or C5-C8 heteroaryl; and C2-C 30 Heteroaryl alkyl groups are preferably C2-C 20 Heteroarylalkyl, such as C4-C 11 Heteroaryl alkyl or C6-C9 heteroaryl alkyl.

[0072] The embodiments will be described in detail below with reference to the accompanying drawings, in which similar reference numerals denote the same or substantially the same or corresponding parts, and redundant descriptions will be omitted. In the drawings, the thickness of layers and regions is enlarged for clarity. Furthermore, in the drawings, the thickness of some layers and regions is enlarged for ease of description. The embodiments described herein are merely examples and various modifications may be made therein.

[0073] [Resistant Composition]

[0074] The resist composition according to the embodiments may include an organometallic compound represented by any one of formulas 1-1 to 1-4, an additive represented by formula 2, and a solvent, wherein the solvent includes a nonpolar solvent, a polar aprotic solvent, or a combination thereof:

[0075]

[0076] Among them, in equations 1-1 to 1-4 and equation 2,

[0077] M 11 It can be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po);

[0078] L 11 To L 14 Each can be a straight-chain, branched, or cyclic C1-C bond, independently of a single bond or substituted or unsubstituted, optionally including heteroatoms. 30 Divalent hydrocarbon groups,

[0079] a11 to a14 can each be independently selected from integers from 1 to 4.

[0080] R 11 To R 14 Each can be independently substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C7-C 30 arylalkyl, substituted or unsubstituted C1-C 30 heteroaryl, or substituted or unsubstituted C2-C 30 heteroarylalkyl,

[0081] R 11 To R 14 Two adjacent elements can optionally be bonded to each other to form a ring.

[0082] b11 to b14 can each be independently selected from integers from 1 to 4.

[0083] Y 11 To Y 13 Each can be independently O, OC (=O), S, SC (=O), NX 14 or NX 14 C(=O),

[0084] X 11 To X 14 Each can independently be hydrogen, deuterium, or a straight-chain, branched, or cyclic C1-C, optionally substituted or unsubstituted, including heteroatoms. 30 Monovalent hydrocarbon groups,

[0085] Y 21 and Y 22 Each can be independently substituted or unsubstituted, optionally including straight-chain, branched, or cyclic C1-C atoms selected as heteroatoms from oxygen, sulfur, nitrogen, and phosphorus atoms. 30 Monovalent hydrocarbon groups,

[0086] L 21 It can be a single bond, a double bond, or a straight-chain, branched, or cyclic C1-C structure, optionally including heteroatoms, with or without substitution. 30 Divalent hydrocarbon groups,

[0087] a21 can be any integer from 1 to 4.

[0088] Y 21 Y 22 and L 21 Two adjacent elements may optionally be bonded to each other to form a fused ring.

[0089] Exposure to high-energy radiation alters the solubility of the resist composition in a developer. The resist composition can be a negative resist composition, wherein the unexposed portions of the resist film are dissolved and removed to form a negative resist pattern, or it can be a positive resist composition, wherein the exposed portions of the resist film are dissolved and removed to form a positive resist pattern. Depending on the exposure intensity and / or the type of developer, the resist composition can be adjusted in various ways, for example, to be negative or positive. For example, the resist composition can be a positive resist composition.

[0090] Additionally, the resist composition according to the embodiments can be used in alkaline developing processes where an alkaline developer is used for developing the resist pattern during formation; or in solvent developing processes where a developer including an organic solvent (hereinafter also referred to as an organic developer) is used for developing the resist pattern. For example, the resist composition can be used in solvent developing processes.

[0091] Since the resist composition is of the non-chemically amplified type, it may substantially exclude photoacid-generating agents.

[0092] Because the physical properties of the organometallic compound change upon exposure to light, the resist composition may substantially exclude compounds having a molecular weight of about 1,000 g / mol or greater, other than the organometallic compound and the additive.

[0093] The organometallic compound and the additive can be prepared by any suitable method, or commercially available products can be used.

[0094] The structure (composition) of the organometallic compounds can be determined by Fourier transform infrared (FT-IR) analysis, NMR analysis, X-ray fluorescence (XRF) analysis, mass spectrometry, ultraviolet (UV) analysis, single-crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC), size exclusion chromatography (SEC) analysis, thermal analysis, etc. Detailed confirmation methods are described in the examples below.

[0095] <Organometallic compounds>

[0096] The molecular weight of the organometallic compound may be about 3000 g / mol or less. For example, the molecular weight of the organometallic compound may be 2000 g / mol or less.

[0097] Although not limited to a specific theory, free radicals can be formed in said organometallic compounds by heat and / or high-energy radiation. For example, organometallic compounds can be decomposed by high-energy radiation, and in particular, by the M-type free radicals of said organometallic compounds. 11 - Carbon bonds form free radicals. Therefore, the physical properties of the organometallic compound, especially its solubility in the developer, can be altered.

[0098] Organometallic compounds represented by any of the chemical formulas 1-1 to 1-4 must include an R group with a relatively low CH bond dissociation energy. 11 To R 14 At least one of these, therefore, the photosensitivity to high-energy radiation, especially EUV, can be improved.

[0099] For example, in equations 1-1 to 1-4, M 11 It can be In, Sn, or Sb. For example, in equations 1-1 to 1-4, M 11 It can be Sn.

[0100] For example, in equations 1-1 to 1-4, L 11 To L 14 Each can be a single bond, substituted or unsubstituted C1-C. 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, or substituted or unsubstituted C1-C 30 Hybrid aryl.

[0101] For example, in equations 1-1 to 1-4, L 11 To L 14 Each can be independently selected from a single bond; and each of the C1-C bonds that are not substituted or are substituted as follows. 30 Alkylene, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkenyl, C6-C 30 aryl and C1-C 30 Heteroaryl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

[0102] For example, in equations 1-1 to 1-4, L 11 To L 14 Each can be independently selected from a single bond; and unsubstituted or replaced by deuterium, halogen, hydroxyl, cyano, C1-C. 20 Alkyl, C1-C 20 Haloalkyl groups or combinations thereof substituted C1-C 30 Alkylene.

[0103] For example, in equations 1-1 to 1-4, a11 to a14 can each be an integer of 1 or 2 independently.

[0104] For example, in equations 1-1 to 1-4, R 11 To R 14 Each can be independently selected from its own unsubstituted or substituted C1-C as follows. 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C20 heteroaryl thiols or combinations thereof.

[0105] For example, in equations 1-1 to 1-4, R 11 To R 14 Each can be independently represented as either C1-C that has not been substituted or has been substituted as follows. 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl and C7-C 30 Arylalkyl: deuterium, halogen atom, cyano, nitro, hydroxyl, thiol group, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

[0106] For example, in equations 1-1 to 1-4, R 11 To R 14 Each can be independently selected from any of the following formulas 3-1 to 3-20:

[0107]

[0108] Among them, in equations 3-1 to 3-20,

[0109] At least one hydrogen atom may optionally be replaced by: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20Halogenated alkoxy groups, C1-C 20 Haloalkylthio groups, or combinations thereof.

[0110] In equations 1-1 to 1-4, b11 to b14 each refer to R. 11 To R 14 The substitution number, for example, in equations 1-1 to 1-4, b11 to b14 can each be 1 or 2 independently.

[0111] R 11 To R 14 Two adjacent elements may optionally be bonded to each other to form a ring.

[0112] For example, multiple R 11 Two adjacent Rs can optionally be bonded to each other to form a ring, and multiple Rs 12 Two adjacent Rs can optionally be bonded to each other to form a ring, and multiple Rs 13 Two adjacent Rs can optionally be bonded to each other to form a ring, and multiple Rs 14 Two adjacent elements may optionally be bonded to each other to form a ring.

[0113] In equations 1-1 to 1-4, Y 11 To Y 13 Each can be independently O, OC (=O), S, SC (=O), NX 14 , or NX 14 C (=O).

[0114] For example, in equations 1-1 to 1-4, Y 11 To Y 13 Each can be independently represented as O, OC (=O), S, or SC (=O).

[0115] For example, in equations 1-1 to 1-4, X 11 To X 14 Each can be independently selected from hydrogen; deuterium; and each of the unsubstituted or substituted C1-C atoms. 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C 30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

[0116] For example, in equations 1-1 to 1-4, X 11 To X 14 Each can be independently selected from hydrogen; deuterium; and each of the unsubstituted or substituted C1-C atoms. 30 Alkyl, C1-C 30 Haloalkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen atom, cyano, nitro, hydroxyl, thiol group, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C1-C20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl groups, or combinations thereof.

[0117] For example, in equations 1-1 to 1-4, X 11 To X 14 Each can be independently selected from hydrogen; deuterium; and C1-C atoms that are either unsubstituted or substituted by deuterium, halogens, or combinations thereof. 30 Alkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C2-C 30 alkynyl group and C6-C 30 Aryl.

[0118] Specifically, in equations 1-1 to 1-4, X 11 To X 14 Each of them may be independently selected from hydrogen; deuterium; and methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, vinyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, ethynyl, phenyl and naphthyl.

[0119] In the embodiments, the organometallic compound represented by any one of formulas 1-1 to 1-4 may be selected from group I of the following:

[0120] <Group I>

[0121]

[0122]

[0123] In group I, n can be an integer from 1 to 4.

[0124] For example, in group I, n can be 2.

[0125] The organometallic compound may be any one of those represented by any one of formulas 1-1 to 1-4 (i.e., used alone), or a mixture of two or more organometallic compounds of formulas 1-1 to 1-4 may be used.

[0126] In the resist composition, based on 100 parts by weight of the resist composition, the organometallic compound may be from about 0.01 parts by weight to about 100 parts by weight, for example 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, 80 or less, 60 or less, 40 or less, 20 or less, 10 or less, 5 or less, or 3 or less by weight.

[0127] <Additives>

[0128] For example, in Equation 2, Y 21 It can be represented by any one of equations 4-1 to 4-5, and Y 22 It can be expressed by any one of equations 4-6 to 4-10:

[0129]

[0130] Among them, in equations 4-1 to 4-10,

[0131] X 41 and X 44 Each can be N or P independently.

[0132] X 42 and X 45 Each can be either O or S independently.

[0133] X 43 and X 46 Each can be independently O, S, N, or P.

[0134] Y in Equations 4-3 and 4-8 41 and Y 42 Each can be independently represented as C or S.

[0135] Y in Equations 4-4 and 4-9 41 and Y 42 Each is P,

[0136] A 41 For containing X 43 C1-C, as a member of the ring 30 Heterocyclic groups,

[0137] A 42 For containing X 46 C1-C, as a member of the ring 30 Heterocyclic groups,

[0138] R 41 To R 44 Each of the following is independently hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, or a straight-chain, branched, or cyclic C1-C group, optionally including heteroatoms, whether substituted or unsubstituted. 30 Monovalent hydrocarbon groups,

[0139] b41 and b42 are each independently selected from integers from 1 to 10, and

[0140] * indicates the bonding site with an adjacent atom.

[0141] In one embodiment, the additive may include those selected from X. 41 To X 43 any one and selected from X 44 To X 46 Any one of them is associated with any metal atom, such as M in formulas 1-1 to 1-4. 11 Coordination can form 5-, 6-, or 7-membered ring structures.

[0142] For example, in equations 4-5 and 4-10, A 41 and A 42 Each independently refers to: i) a monovalent group derived from a first ring, ii) a monovalent group derived from a fused ring in which two or more first rings are fused together, or iii) a monovalent group derived from a fused ring in which one or more first rings and one or more second rings are fused together.

[0143] The first ring may be tetrahydropyran, dihydropyran, pyran, tetrahydrothiaran, dihydrothiaran, thiaran, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine, or triazine, and

[0144] The second ring may be cyclopentane, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, or naphthalene.

[0145] For example, in equations 4-5 and 4-10, A 41 and A 42 Each can be independently: i) a monovalent group derived from the first ring, ii) a monovalent group derived from a fused ring in which two or more first rings are fused together, or iii) a monovalent group derived from a fused ring in which one or more first rings and one or more second rings are fused together.

[0146] The first ring may be tetrahydropyran, dihydropyran, pyran, tetrahydrothiaran, dihydrothiaran, thiaran, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine, or triazine; and

[0147] The second ring can be benzene.

[0148] For example, in equations 4-1 to 4-10, R 41 To R44 Each group can be independently selected from hydrogen; deuterium; halogen; cyano; nitro; hydroxyl; thiol group; amino; carboxyl group; and each of the following C1-C groups, either unsubstituted or substituted: 30 Alkyl, C1-C 30 Haloalkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

[0149] For example, in equations 4-1 to 4-10, R 41 To R 44 Each group can be independently selected from hydrogen; deuterium; halogen; cyano; nitro; hydroxyl; thiol group; amino; carboxyl group; and each of the following C1-C groups, either unsubstituted or substituted: 30 Alkyl, C1-C 30 Haloalkyl, C3-C 30 cycloalkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl groups, or combinations thereof.

[0150] In one implementation, in equation 2, i)Y 21 It can be represented by Equation 4-5, and Y 22 It can be represented by any one of equations 4-6 to 4-10, or

[0151] ii)Y 21 It can be represented by any one of equations 4-1 to 4-5, and Y 22 It can be represented by Equation 4-10.

[0152] In another embodiment, in Equation 2, Y 21 It can be represented by Equation 4-5, and Y 22 It can be represented by Equation 4-10.

[0153] For example, in Equation 2, L 21 C1-C can be a single bond, a double bond, substituted or unsubstituted. 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, or substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, or substituted or unsubstituted C1-C 30 Hybrid aryl.

[0154] For example, in Equation 2, L 21 Options include single bonds; double bonds; and C1-C, which are either not replaced or replaced by the following: 30 Alkylene, C3-C 30 Cycloalkylene, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkylene, C3-C 30Heterocyclic alkenyl, C6-C 30 aryl and C1-C 30 Heteroaryl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

[0155] For example, in Equation 2, L 21 Options include single bonds; double bonds; and C1-C, which are either not replaced or replaced by the following: 30 Alkylene and C2-C 30 Imenoyl groups: deuterium, halogen, hydroxyl, cyano, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl groups or combinations thereof.

[0156] In an implementation, the additive can be represented by formula 2-1:

[0157]

[0158] In Equation 2-1,

[0159] For X 43 X 46 A 41 A 42 L 21 a21, R 41 R 43 For descriptions of b41 and b42, please refer to the foregoing details.

[0160] In an embodiment, the additive may be represented by the following formula 2-11 or 2-12:

[0161]

[0162] In equations 2-11 and 2-12,

[0163] X 43 and X 46 Each can be independently O, S, N, or P.

[0164] A 41 It can contain X 43 C1-C, as a member of the ring 30 Heterocyclic groups,

[0165] A 42 For containing X 46 C1-C, as a member of the ring 30 Heterocyclic groups,

[0166] Z 21 and Z 22 Each can be either C or N independently.

[0167] Z 21 and Z 22 The key between them can be a single key or a double key.

[0168] L 22 Options include single bonds; double bonds; and C1-C, which are either not replaced or replaced by the following: 30 Alkylene and C2-C 30 Imenoyl groups: deuterium, halogen, hydroxyl, cyano, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl groups or combinations thereof,

[0169] a22 can be any integer from 1 to 4.

[0170] R 41 and R 43 Each can be independently substituted or unsubstituted, optionally including heteroatoms, of straight-chain, branched, or cyclic C1-C. 30 Monovalent hydrocarbon groups, and

[0171] b41 and b42 can each be independently selected from integers from 1 to 10.

[0172] In equations 2-11 and 2-12, X 43 and Z 21 The bond between and Z 22 and X 46 The bonds between them can be either single or double bonds.

[0173] For example, in equations 2-11 and 2-12, in X 43 and X 46 There can be three chemical bonds between them, and these three chemical bonds include X. 43and Z 21 Chemical bonds between them, Z 21 and Z 22 The chemical bonds between them, and Z 22 and X 46 The chemical bonds between them.

[0174] In an implementation, the additive may be represented by any one of formulas 2-21 to 2-26:

[0175]

[0176]

[0177] Among them, in equations 2-21 to 2-26,

[0178] X 43 and X 46 Each can be independently O, S, N, or P.

[0179] A 41 For containing Z 21 X 43 W 41 To W 44 and W 49 C1-C, as a member of the ring 30 Heterocyclic groups,

[0180] A 42 For containing Z 22 X 46 W 45 To W 48 and W 50 C1-C, as a member of the ring 30 Heterocyclic group, Z 21 and Z 22 Each can be independently represented as C or N.

[0181] W 41 To W 44 and W 49 Each independently is C(R) 41a ), C(R 41a (R) 41b ), or N, W 45 To W 48 and W 50 Each independently is C(R) 43a ), C(R 43a (R) 43b ), or N,

[0182] In Z 21 With Z 22 The key between Z 21 With X 43The key between, in X 43 With W 41 The key between, in W 41 With W 42 The key between, in Z 21 With W 43 The key between, in W 43 With W 44 The key between, in Z 22 With X 46 The key between, in X 46 With W 45 The key between, in W 45 With W 46 The key between, in Z 22 With W 47 The key between, in W 47 With W 48 The key between, in W 44 With W 49 The key between, in W 49 With Z 21 The key between, in Z 22 With W 50 The key between, in W 48 With W 50 The key between, in W 42 With W 43 The key between, in W 46 With W 47 The key between, in W 42 With W 49 The key between, and in W 46 With W 50 Each of the bonds between them is either a single bond or a double bond;

[0183] L 22 Selected from single bonds; double bonds; and C1-C bonds that are not substituted or are substituted as follows: 30 Alkylene and C2-C 30 Imenoyl groups: deuterium, halogen, hydroxyl, cyano, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl groups or combinations thereof,

[0184] a22 is selected from integers from 1 to 4.

[0185] R 41 R 43 R 41a R 41b R 43a and R 43b Each is independently a straight-chain, branched, or cyclic C1-C, optionally including heteroatoms, whether substituted or unsubstituted. 30 Monovalent hydrocarbon groups, and

[0186] b41 and b42 are each independently selected from integers from 1 to 10.

[0187] In an implementation, the additive may be represented by any one of formulas 2-31 to 2-48:

[0188]

[0189] Among them, in equations 2-31 to 2-48,

[0190] At least one hydrogen atom may optionally be replaced by: deuterium, halogen, cyano, nitro, hydroxyl, thiol group, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C3-C 20 cycloalkyl, C2-C 20 alkenyl, C3-C 20 Cycloalkenyl, C3-C 20 Heterocyclic alkenyl, C2-C 20 alkynyl group, C6-C 20 Aryl, C7-C 20 arylalkyl, C1-C 20 heteroaryl, C2-C 20 Heteroarylalkyl groups, or combinations thereof, and

[0191] At least one carbon and nitrogen may optionally combine with an adjacent carbon or nitrogen to form a ring.

[0192] In this embodiment, the additive may be selected from group II of the following:

[0193] Group II

[0194]

[0195] The additive may include N, O, S and / or P, which provide lone pairs of electrons, enabling coordination bonding with the organometallic compound, thereby enhancing the chemical stability of the organometallic compound.

[0196] Therefore, the resist composition containing the additive can significantly reduce the hydrolysis and / or fusion reaction of the organometallic compound, and by controlling the properties of the solvent and / or developer used, such as polarity, the resist composition can be a positive resist composition.

[0197] The additive may be any one represented by Formula 2, or a mixture of two or more may be used.

[0198] In the resist composition, based on 100 parts by weight of the resist composition, the additive may be from about 0.01 parts by weight to about 100 parts by weight, for example 0.1 or more, 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, 80 or less, 60 or less, 40 or less, 20 or less, 10 or less, 5 or less, 4 or less, 3 or less, or 2 or less by weight. If the ranges described above are satisfied, the chemical bonds between the organometallic compounds can be sufficiently formed and side reactions are suppressed, thereby providing a resist composition with improved sensitivity and / or resolution.

[0199] In the resist composition, the additive may be included in an amount from about 0.1 parts by weight to about 100,000 parts by weight based on 100 parts by weight of the organometallic compound. For example, the additive may be included in an amount from about 10 parts by weight to about 1,000 parts by weight, such as from about 20 parts by weight to about 100 parts by weight, from about 30 parts by weight to about 80 parts by weight, from about 35 parts by weight to about 60 parts by weight, or from about 40 parts by weight to about 50 parts by weight based on 100 parts by weight of the organometallic compound. If the ranges described above are satisfied, the resist composition can significantly improve storage stability while maintaining the photosensitivity at the level of a resist composition without the additive.

[0200] Solvent

[0201] Solvents can be used alone or in combination of two or more different types.

[0202] The solvent may include nonpolar solvents, polar aprotic solvents, or combinations thereof.

[0203] For example, the solvent may be a polar aprotic solvent.

[0204] Nonpolar solvents may include ether-based solvents, hydrocarbon-based solvents, and combinations thereof.

[0205] Polar aprotic solvents may include ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and combinations thereof.

[0206] Examples of ether-based solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; cyclic ether solvents such as 1,4-dioxane, tetrahydrofuran, and tetrahydropyran; and ether solvents containing aromatic rings such as diphenyl ether and anisole.

[0207] Examples of ketone-based solvents include linear ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, and trimethylnonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, and methylcyclohexanone; and other ketone solvents such as 2,4-pentanedione, acetone-acetone, and acetophenone.

[0208] Examples of amide-based solvents include cyclic amide-based solvents such as N,N'-dimethylimidazolium ketone and N-methyl-2-pyrrolidone; and linear amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide and N-methylpropionamide.

[0209] Examples of ester-based solvents include acetate solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate; and polyol-containing ether carboxylic acid ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol mono-n-butyl ether acetate. Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; and other solvents such as ethylene glycol diacetate, methoxytriethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

[0210] Examples of sulfoxide-based solvents include dimethyl sulfoxide and diethyl sulfoxide.

[0211] Examples of hydrocarbon-based solvents include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, and isooctane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene.

[0212] For example, the solvent may be selected from ketone-based solvents, ester-based solvents, and combinations thereof.

[0213] For example, the solvent may be selected from solvents based on linear ketones, solvents based on cyclic ketones, solvents based on ether carboxylic esters containing polyols, solvents based on lactones, solvents based on acetates, and combinations thereof.

[0214] Specifically, the solvent may be selected from methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, and combinations thereof.

[0215] The resist composition may be substantially water-free, and therefore the solvent may also be water-free. For example, the resist composition may contain 3% by weight or less water, and the solvent may contain 3% by weight or less water.

[0216] Based on 100 parts by weight of the resist composition, the solvent may be used in amounts from about 0 parts by weight to about 99.9 parts by weight, for example from about 60 parts by weight to about 99 parts by weight, from about 80 parts by weight to about 98 parts by weight, or from about 90 parts by weight to about 97 parts by weight. The solvent may be used alone or in combination of two or more different types.

[0217] <Optional Components>

[0218] When necessary, the resist composition may further include surfactants, crosslinking agents, leveling agents, colorants, or combinations thereof.

[0219] The resist composition may further include a surfactant to improve properties such as coating and developing. Specific examples of surfactants include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. The surfactant may be commercially available or synthetically manufactured. Examples of commercially available surfactants include KP341 (a product of Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75 and Polyflow No. 95 (products of Mitsubishi Materials Electronic Chemicals Co., Ltd.), F-Top EF301, F-Top EF303, and F-Top EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), and MEGAFACE. F171, MEGAFACE F173, R40, R41, R43 (products of DIC Corporation), Fluorad FC430 and Fluorad FC431 (a 3M product), AsahiGuard AG710 (a product of AGC Inc.), and Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, and Surflon SC-106 (products of AGC Seimi Chemical Co., Ltd.).

[0220] Based on 100 parts by weight of the resist composition, the surfactant may be included in an amount from about 0 parts by weight to about 20 parts by weight. The surfactant may be used alone or in combination of two or more different types.

[0221] The method for preparing the resist composition is not particularly limited and may include, for example, mixing the organometallic compound, the additive represented by Formula 2, and any optional components in an organic solvent. There are no particular limitations on the mixing temperature and duration. Filtration may be performed after mixing if necessary.

[0222] [Pattern Formation Method]

[0223] In the following text, reference will be made to Figure 1 and 2A The pattern forming method according to the example implementation is described in more detail in section 2C. Figure 1 To illustrate the pattern forming method according to an example implementation, and Figures 2A to 2C This is a side cross-sectional view showing a pattern forming method according to an exemplary embodiment. Hereinafter, a method for forming a pattern using a negative resist composition will be described as an example, but is not limited thereto.

[0224] Reference Figure 1 The pattern forming method includes applying a resist composition to form a resist film (S101), exposing at least a portion of the resist film to high-energy rays (S102), and developing the exposed resist film using a developer (S103).

[0225] First, a substrate 100 is prepared. The substrate 100 may be, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, or copper. In some embodiments, the substrate 100 may include III-V compounds such as GaP, GaAs, GaSb, etc.

[0226] The resist composition can be applied to the substrate 100, for example, by a coating method to form a resist film 110 of a desired thickness. If necessary, the resist film 110 can be heated (pre-baked, PB) to remove any residual organic solvents. Alternatively, heating the resist film 110 can generate free radicals, and subsequent exposure can allow these free radicals to chemically bond, forming crosslinks.

[0227] The coating method can include spin coating, dip coating, roller coating, or other common coating methods. Among these, spin coating is particularly useful, and by adjusting the viscosity, concentration, and / or rotation speed of the resist composition, a resist film 110 of desired thickness can be formed. For example, the thickness of the resist film 110 can be from about 10 nm to about 300 nm. For example, the thickness of the resist film 110 can be from about 30 nm to about 200 nm.

[0228] The lower limit of the pre-baking temperature can be 60°C or higher, for example, 80°C or higher. The upper limit of the pre-baking temperature can be 150°C or lower, for example, 140°C or lower. The lower limit of the pre-baking time can be 5 seconds or more, for example, 10 seconds or more. The upper limit of the pre-baking time can be 600 seconds or less, for example, 300 seconds or less.

[0229] Before applying the resist composition to the substrate 100, a sacrificial layer (not shown) for etching purposes may also be formed on the substrate 100. The sacrificial layer can refer to a layer in which an image is transferred from the resist pattern, thereby transforming it into a desired pattern. In embodiments, the sacrificial layer may be formed comprising an insulating material, such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the sacrificial layer may be formed comprising a conductive material, such as a metal, metal nitride, metal silicide, or metal silicon nitride. In some embodiments, the sacrificial layer may be formed comprising a semiconductor material, such as polysilicon.

[0230] In this embodiment, an anti-reflective film may be further formed on the substrate 100 to improve or maximize the efficiency of the resist. The anti-reflective film may be an organic or inorganic anti-reflective film.

[0231] In an embodiment, a protective film may be further provided on the resist film 110 to reduce the impact of alkaline impurities included during the process. Additionally, when immersion exposure is performed, for example, a protective film for immersion may be provided on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0232] Next, at least a portion of the resist film 110 can be exposed to high-energy radiation. For example, high-energy radiation passing through the mask 120 can be irradiated onto at least a portion of the resist film 110. For this reason, the resist film 110 may have an exposed portion 111 and an unexposed portion 112.

[0233] Although not limited to a specific theory, the generation of free radicals in the exposed portion 111 through exposure and the formation of chemical bonds between the free radicals can alter the physical properties of the resist composition.

[0234] In some cases, exposure can be performed by using a liquid, such as water, as a medium to irradiate a patterned mask with high-energy rays. Examples of high-energy rays can include electromagnetic waves such as ultraviolet, deep ultraviolet, extreme ultraviolet (EUV) (wavelength 13.5 nm), X-rays, and gamma rays; as well as charged particle beams such as electron (EB) beams and alpha particle beams. Irradiation with these high-energy rays can be collectively referred to as "exposure".

[0235] Various light sources can be used for exposure. For example, sources emitting laser beams in the UV range, such as KrF excimer lasers (248 nm wavelength), ArF excimer lasers (193 nm wavelength), and F2 excimer lasers (157 nm wavelength), can be used. Sources emitting harmonic laser beams in the far ultraviolet or vacuum ultraviolet range can be used by converting the wavelength of the laser beam received from a solid-state laser source (YAG or semiconductor laser). Sources emitting EB or EUV can also be used. During exposure, exposure is typically performed using a mask corresponding to the desired pattern; however, when the light being exposed is EB, exposure can be performed by direct writing without using a mask.

[0236] The integrated dose of high-energy radiation, for example, when extreme ultraviolet radiation is used as the high-energy radiation, can be 2000 mJ / cm². 2 Or even smaller, for example, 500 mJ / cm 2 Or even smaller. Additionally, when using EB as a high-energy ray, the integrated dose can be 5,000 μC / cm². 2 Or smaller, or 1,000 μC / cm 2 Or smaller.

[0237] The lower limit of the PEB temperature can be 50°C or higher, for example, 80°C or higher. The upper limit of the PEB temperature can be 250°C or lower, for example, 200°C or lower. The lower limit of the PEB time can be 5 seconds or more, for example, 10 seconds or more. The upper limit of the PEB time can be 600 seconds or less, for example, 300 seconds or less.

[0238] Next, the exposed resist film 110 can be developed using a developer. The exposed portions 111 can be removed by being washed away with the developer, while the unexposed portions 112 can be retained without being washed away with the developer.

[0239] Examples of the developer include alkaline developers and developers containing organic solvents (hereinafter also referred to as "organic developers"). Examples of developing methods include immersion, puddle, spray, dynamic injection, etc. The developing temperature may be, for example, about 5°C or higher and about 60°C or lower, and the developing time may be, for example, about 5 seconds or more and about 300 seconds or less.

[0240] The alkaline developer may include, for example, an alkaline aqueous solution in which one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, ethyl dimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN) are dissolved. The alkaline developer may further include a surfactant.

[0241] The lower limit of the amount of the alkaline compound included in the alkaline developer may be 0.1% by weight or more, or 0.5% by weight or more, or 1% by weight or more. Furthermore, the upper limit of the amount of the alkaline compound included in the alkaline developer may be 20% by weight or less, or 10% by weight or less, or 5% by weight or less.

[0242] Examples of organic solvents included in the organic developer may include the same organic solvents described in the <Solvents> section of [Resist Composition]. Alternatively, alcohol-based solvents or lactate-based solvents may be used as organic solvents.

[0243] Examples of alcohol-based solvents include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, 4-methyl... -2-Pentanol (MIBC), sec-Heptanol, 3-Heptanol, n-Octanol, 2-Ethylhexanol, sec-Octanol, n-Nonanol, 2,6-Dimethyl-4-Heptanol, n-Decanol, sec-Undecanool, Trimethylnonanol, sec-Tetradecanool, sec-Heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-Trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyol solvents such as ethylene glycol, 1,2-propanediol, 1, 3-Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol; and ether solvents including polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and ethylene glycol monobenzene. 2-Ethyl Butyl Glycol Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monopropyl Ether, Diethylene Glycol Monobutyl Ether, Diethylene Glycol Monohexyl Ether, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Monoethyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, and Dipropylene Glycol Monopropyl Ether.

[0244] Examples of lactate-based solvents include methyl lactate, ethyl lactate, n-butyl lactate, and n-pentyl lactate.

[0245] For example, nBA (n-butyl acetate), PGME, PGMEA, ethyl lactate, GBL (gamma-butyrolactone), and IPA (isopropanol) can be used as organic developers. These organic developers may further include organic acids such as acetic acid, formic acid, and citric acid.

[0246] The lower limit of the organic solvent content in the organic developer may be 80% by weight or more, for example 90% by weight or more, 95% by weight or more, or 99% by weight or more.

[0247] Organic developers may also include surfactants. Additionally, organic developers may include trace amounts of water. Furthermore, the development process can be stopped during development by replacing the organic developer with a different type of solvent.

[0248] The resist pattern can be further cleaned after development. Cleaning solutions (cleaning fluids) such as ultrapure water and rinsing solutions (rinsing fluids) can be used. There are no particular limitations on the rinsing solution, as long as it does not dissolve the resist pattern, and solutions containing common organic solvents can be used. For example, the rinsing solution can be an alcohol-based solvent or an ester-based solvent. After cleaning, any residual rinsing solution on the substrate and pattern can be removed. When using ultrapure water, any residual water on the substrate and pattern can be removed.

[0249] In addition, developers can be used alone or in combination of two or more types.

[0250] As described above, after forming the resist pattern, a patterned wiring substrate can be obtained by etching. The etching method can be carried out using known methods such as dry etching using plasma gas and wet etching using alkaline solutions, copper(II) chloride solutions or ferric(III) chloride solutions.

[0251] After the resist pattern is formed, plating can also be performed. There are no particular restrictions on the plating method, but examples include copper plating, solder plating, nickel plating, and gold plating.

[0252] Organic solvents can be used to remove residual resist patterns after etching. Examples of such organic solvents include, but are not limited to, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The removal method is not particularly limited and may include, for example, immersion and spraying methods. Furthermore, the wiring substrate with the resist pattern formed may be a multilayer wiring substrate and may have small-diameter vias.

[0253] In one embodiment, the wiring substrate is formed by depositing metal in a vacuum after forming a resist pattern, and then dissolving the resist pattern in a solution; this method is called a stripping method.

[0254] Figures 3A to 3E This is a side cross-sectional view showing a method for forming a patterned structure according to an embodiment.

[0255] like Figure 3A As shown, a material layer 130 may be formed on the substrate 100 before the resist film 110 is formed on the substrate 100. The resist film 110 may be formed on the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some embodiments, the material layer 130 may have a multilayer structure. The material of the material layer 130 may be different from the material of the substrate 100.

[0256] like Figure 3BAs shown, the resist film 110 may undergo a pre-baking process before exposure, and then be exposed to high-energy rays through a mask 120, and subsequently the resist film 110 may include an exposed portion 111 and an unexposed portion 112.

[0257] like Figure 3C As shown, the exposed resist film 110 can be developed using a developer. The exposed portion 111 can be washed away by the developer, while the unexposed portion 112 remains intact, thereby forming the resist pattern 115.

[0258] like Figure 3D As shown, the resist pattern 115 can be used as a mask to etch exposed portions of the material layer 130 to form the material pattern 135 on the substrate 100.

[0259] like Figure 3E As shown, the resist pattern 115 can be removed.

[0260] Figures 4A to 4E This is a side cross-sectional view showing a method for forming a semiconductor device according to an embodiment.

[0261] like Figure 4A As shown, a gate dielectric 505 (e.g., silicon oxide) may be formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0262] like Figure 4B As shown, a resist pattern 540b can be formed on the hard mask layer 520. The resist pattern 540b can be formed using a resist composition according to an embodiment. The resist composition may include an organic solvent.

[0263] like Figure 4C As shown, the hard mask layer 520, the gate layer 515, and the gate dielectric 505 can be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0264] like Figure 4D As shown, the hard mask pattern 520a may optionally be removed, and spacer layers may be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layers may be formed using a deposition process (e.g., CVD). The spacer layers may be etched to form spacers 535a (e.g., silicon nitride) on the sidewalls of the gate electrode pattern 515a and the gate dielectric pattern 505a. After the spacers 535a are formed, ions may be implanted into the substrate 500 to form source / drain impurity regions (S / D).

[0265] like Figure 4EAs shown, an interlayer insulating film 560 (e.g., oxide) may be formed on substrate 500, covering gate electrode pattern 515a, gate dielectric pattern 505a, and spacer 535a. Subsequently, the interlayer insulating film 560 may have electrical contacts 570a, 570b, and 570c formed to connect with the gate electrode pattern 515a and the S / D region. The electrical contacts 570a, 570b, and 570c may be formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c.

[0266] Figures 4A to 4E Examples of transistors are shown, but this disclosure is not limited thereto.

[0267] For example, although not in Figure 4D and 4E As shown, however, in some embodiments, the hard mask pattern 520a may not be removed before forming the spacer 535a. For example, if the hard mask pattern 520a is not removed, it may be retained in the [image / image / description]. Figure 4D and 4E On top of the gate electrode pattern 515a, the spacer 535a can cover Figure 4D and 4E The hard mask pattern 520a has a sidewall, and the electrical contact 570b can extend through the opening in the hard mask pattern 520a to directly contact the upper surface of the gate electrode pattern 515a.

[0268] The resist composition according to the embodiments can also be used in patterning processes for forming other types of semiconductor devices.

[0269] The present disclosure will be described in more detail using the following embodiments and comparative examples, but the technical scope of the present disclosure is not limited to the following embodiments.

[0270] [Example]

[0271] Synthesis Example 1: Synthesis of SM1

[0272]

[0273] 8.2 g (69.2 mmol) of Sn powder and 120 mL of dry toluene were placed in a 250 mL three-necked flask, and the temperature was raised to 90 °C. After adding approximately 1.0 mL of DI (deionized water), 10.0 g (69.2 mmol) of 4-fluorobenzyl chloride was added dropwise over 10 minutes. The mixture was then heated with stirring and refluxed at 130 °C for 4 hours, and unreacted Sn powder was filtered off using a Buchner funnel. Simultaneously, as the filtered solution cooled, the product was obtained in 6.5 g (36% yield): a white crystalline SM1 precursor.

[0274]

[0275] 1.5 g (3.7 mmol) of SM1 precursor and 21.0 mL of dry acetone were placed in a 50 mL single-necked flask, and the temperature was lowered to 0 °C. After adding 0.6 g (7.4 mmol) of sodium acetate, the mixture was stirred for approximately 12 hours. The NaCl salt formed in the solution was filtered through a 0.45 μm filter, and the filtered solution was then concentrated by rotary evaporation and dried under vacuum to give 1.6 g of SM1 (74% yield).

[0276] 1 H-NMR (500MHz, DMSO-d6): δ~6.9(8H),~2.6(4H),~1.6(6H)

[0277] Evaluation Example 1: Thin Film Development Evaluation

[0278] (1) Terminology

[0279] In Examples 1-1 and 2-1 to 2-5, E0 refers to the exposure dose at which the film is fully developed (discovered) (without further reduction in thickness), while E1 refers to the exposure dose at which the film begins to develop.

[0280] In Comparative Example 1-1, E0 refers to the exposure dose at which the film begins to harden, and E1 refers to the exposure dose at the saturation point where the film thickness no longer increases.

[0281] γ (gamma) is the value calculated using the contrast curve according to Equation 1 below.

[0282] <Equation 1>

[0283]

[0284] (2) Evaluation of thin film development

[0285] SM1 obtained in Synthesis Example 1 was dissolved in cyclopentanone at a concentration of 2% by weight, and compound A was added as an additive to the solution at a mass ratio of SM1:compound A = 2.5:1 to obtain casting solution C-1. Casting solution C-2 was prepared with the same composition as casting solution C-1, except that compound A was not added. Casting solutions D-1 to D-5 were prepared with the same composition as casting solution C-1, except that the solvents listed in Table 2 were used instead of cyclopentanone. A silicon wafer with a diameter of 4 inches was treated with O2 plasma for 30 minutes, and then casting solutions C-1, C-2, and D-1 to D-5 were spin-coated onto the silicon wafer at 1200 rpm for 1 minute, followed by drying (PAB) at 90°C for 1 minute to produce films with the initial thicknesses shown in Table 1. Then, a jig with a thickness of 3.5 mm and rectangular holes (1 cm x 1 cm, arranged in a 4 x 4 grid) is placed on the film, and each hole is exposed to a dose range of 0 mJ / cm. 2 Up to 100mJ / cm 2 The film was exposed to DUV light (254 nm wavelength) and dried at 150°C (PEB) for 3 minutes. The dried film was then immersed in a PGME:PGMEA (99.5:0.5 volume / volume) developer at 25°C for 60 seconds, and the remaining film thickness was measured and is shown in Tables 1 and 2.

[0286] [Table 1]

[0287]

[0288] [Table 2]

[0289]

[0290]

[0291] Refer to Table 1 and Figure 5A and 5B This confirms that Examples 1-1 exhibit the characteristics of a positive resist composition. In contrast, Comparative Example 1-1 exhibits characteristics less than 30 mJ / cm². 2 At DUV exposure doses, no crosslinking occurred, resulting in the entire film being washed away by the developer. However, at doses greater than 30 mJ / cm², the film did not undergo crosslinking. 2 At the DUV exposure dose, crosslinking occurs, and the film is not washed away by the developer, thus confirming that Comparative Example 1-1 exhibits the characteristics of a negative resist composition.

[0292] Refer to Table 2 and Figures 6A to 6E This confirms that Examples 2-1 to 2-5 each exhibit the characteristics of a positive resist composition.

[0293] Embodiments of this disclosure may provide resist compositions with improved storage stability and enhanced sensitivity, thereby providing patterns with improved resolution.

[0294] It should be understood that the embodiments described herein are to be considered in a descriptive sense only and are not intended for limiting purposes. The descriptions of features or aspects in each embodiment should typically be considered applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, those skilled in the art will understand that various changes in form and detail may be made therein without departing from the spirit and scope defined by the appended claims.

Claims

1. A resist composition comprising: an organometallic compound represented by any one of Formulas 1-1 to 1-4; an additive represented by Formula 2; and a solvent; wherein the solvent includes a nonpolar solvent, a polar aprotic solvent, or a combination thereof, wherein, in Formulas 1-1 to 1-4 and 2, M 11 The constituent elements are indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po). L 11 To L 14 Each of the following is an independent straight-chain, branched, or cyclic C1-C bond, either single-bonded or substituted or unsubstituted, optionally including heteroatoms. 30 Divalent hydrocarbon groups, a11 to a14 are each independently an integer selected from 1 to 4, R 11 To R 14 Each is independently either substituted or unsubstituted C1-C 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Heterocyclic alkyl, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocyclic alkenyl, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C7-C 30 arylalkyl, substituted or unsubstituted C1-C 30 heteroaryl, or substituted or unsubstituted C2-C 30 heteroarylalkyl, R 11 To R 14 Two adjacent elements may be optionally bonded to each other to form a ring. b11 to b14 are each independently an integer selected from 1 to 4, Y 11 To Y 13 Each is independently represented as O, OC (=O), S, SC (=O), NX 14 , or NX 14 C(=O), X 11 To X 14 Each is independently hydrogen, deuterium, or a straight-chain, branched, or cyclic C1-C, optionally substituted or unsubstituted, including heteroatoms. 30 Monovalent hydrocarbon groups, Y 21 and Y 22 Each is independently a straight-chain, branched, or cyclic C1-C atom, either substituted or unsubstituted, including at least one heteroatom selected from oxygen, sulfur, nitrogen, and phosphorus atoms. 30 Monovalent hydrocarbon groups, L 21 Straight-chain, branched, or cyclic C1-C bonds, either single or double, or optionally substituted or unsubstituted, including heteroatoms. 30 Divalent hydrocarbon groups, a21 is an integer selected from 1 to 4, and Y 21 Y 22 and L 21 Two adjacent elements are optionally bonded to each other to form a fused ring.

2. The resist composition according to claim 1, Where M 11 It can be In, Sn, or Sb.

3. The resist composition according to claim 1, Where R 11 To R 14 Each is independently selected from its own unsubstituted or substituted C1-C as follows 30 Alkyl, C3-C 30 cycloalkyl, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C7-C 30 arylalkyl, C1-C 30 heteroaryl and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

4. The resist composition according to claim 1, the organometallic compound is represented by one of Formulas 1-1 to 1-3, Where Y 11 To Y 13 Each can be independently O, OC (=O), S, or SC (=O), and X 11 To X 14 Each is independently selected from: hydrogen; deuterium; and each of the following C1-C atoms, either unsubstituted or substituted: 30 Alkyl, C1-C 30 Haloalkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy groups, C1-C 30 Haloalkylthio group, C3-C 30 cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocyclic alkyl, C2-C 30 alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocyclic alkenyl, C2-C 30 alkynyl group, C6-C 30 Aryl, C6-C 30 Aryloxy group, C6-C 30 Arylthio, C7-C 30 arylalkyl, C1-C 30 heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 heteroaryl thiols and C2-C 30 Heteroarylalkyl groups: deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sulopentalide moiety, carboxylic anhydride moiety, C1-C 20 Alkyl, C1-C 20 Haloalkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy groups, C1-C 20 Haloalkylthio group, C3-C 20 cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 heteroaryl, C6-C 20 Aryloxy group, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroaryl thiols or combinations thereof.

5. The resist composition according to claim 1, wherein the organometallic compound represented by any one of Formulas 1-1 to 1-4 is selected from the following Group I: <Group I> in, In Group I, n is an integer from 1 to 4.

6. The resist composition according to claim 1, Where Y 21 Any one of equations 4-1 to 4-5, and Y 22 Any one of equations 4-6 to 4-10: in, in Formulas 4-1 to 4-10, X 41 and X 44 Each can be N or P independently. X 42 and X 45 Each can be either O or S independently. X 43 and X 46 Each can be independently O, S, N, or P. Y in Equations 4-3 and 4-8 41 and Y 42 Each can be independently represented as C or S. Y in Equations 4-4 and 4-9 41 and Y 42 Each is P, A 41 For containing X 43 C1-C, as a member of the ring 30 Heterocyclic groups, A 42 For containing X 46 C1-C, as a member of the ring 30 Heterocyclic groups, R 41 To R 44 Each of the following is independently hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, thiol, amino, carboxyl, or a straight-chain, branched, or cyclic C1-C group, optionally including heteroatoms, whether substituted or unsubstituted. 30 Monovalent hydrocarbon groups, b41 and b42 are each independently an integer selected from 1 to 10, and * is a bonding site to an adjacent atom.

7. The resist composition according to claim 6, Where A 41 and A 42 Each is independently a monovalent group derived from a first ring, a monovalent group derived from a fused ring in which two or more of the first rings are fused together, or a monovalent group derived from a fused ring in which one or more of the first rings and one or more of the second rings are fused together. the first ring is tetrahydropyran, dihydropyran, pyran, tetrahydrothiopyran, dihydrothiopyran, thiopyran, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine or triazine; and the second ring is cyclopentane, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene or naphthalene.

8. The resist composition according to claim 1, wherein the additive is represented by the following Formula 2-1: in, In Formula 2-1, X 43 and X 46 Each can be independently O, S, N, or P. A 41 For containing X 43 C1-C, as a member of the ring 30 Heterocyclic groups, A 42 For containing X 46 C1-C, as a member of the ring 30 Heterocyclic groups, L 21 Straight-chain, branched, or cyclic C1-C bonds, either single or double, or optionally substituted or unsubstituted, including heteroatoms. 30 Divalent hydrocarbon groups, a21 is an integer from 1 to 4, R 41 and R 43 Each is independently a straight-chain, branched, or cyclic C1-C, optionally including heteroatoms, whether substituted or unsubstituted. 30 Monovalent hydrocarbon groups, b41 and b42 are each independently an integer selected from 1 to 10, and R 41 R 43 and L 21 Two adjacent elements are optionally bonded to each other to form a fused ring.

9. The resist composition according to claim 1, wherein the additive is represented by any one of Formulas 2-21 to 2-26: in, In Formulas 2-21 to 2-26, X 43 and X 46 Each can be independently O, S, N, or P. A 41 For containing Z 21 X 43 W 41 To W 42 and selected from W 43 W 44 and W 49 One or two C1-C members as ring members 30 Heterocyclic groups, A 42 For containing Z 22 X 46 W 45 To W 46 and selected from W 47 W 48 and W 50 One or two C1-C members as ring members 30 Heterocyclic groups, Z 21 and Z 22 Each can be independently represented as C or N. W 41 To W 44 and W 49 Each independently is C(R) 41a ), C(R 41a (R) 41b ), or N, W 45 To W 48 and W 50 Each independently is C(R) 43a ), C(R 43a (R) 43b ), or N, In Z 21 With Z 22 The key between, in Z 21 With X 43 The key between, in X 43 With W 41 The key between, in W 41 With W 42 The key between, in Z 21 With W 43 The key between, in W 43 With W 44 The key between, in Z 22 With X 46 The key between, in X 46 With W 45 The key between, in W 45 With W 46 The key between, in Z 22 With W 47 The key between, in W 47 With W 48 The key between, in W 44 With W 49 The key between, in W 49 With Z 21 The key between, in Z 22 With W 50 The key between, in W 48 With W 50 The key between, in W 42 With W 43 The key between, in W 46 With W 47 The key between, in W 42 With W 49 The key between, and in W 46 With W 50 Each of the bonds between them is either a single bond or a double bond; L 22 Selected from: single bonds; double bonds; and C1-C bonds that are not substituted or are substituted as follows. 30 Alkylene and C2-C 30 Imenoyl groups: deuterium, halogen, hydroxyl, cyano, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl groups or combinations thereof, a22 is an integer selected from 1 to 4, R 41 R 43 R 41a R 41b R 43a and R 43b Each is independently a straight-chain, branched, or cyclic C1-C, optionally including heteroatoms, whether substituted or unsubstituted. 30 Monovalent hydrocarbon groups; and b41 and b42 are each independently an integer selected from 1 to 10.

10. The resist composition according to claim 1, wherein the additive is selected from the following Group II: <Group II> 11. The resist composition according to claim 1, wherein based on 100 parts by weight of the organometallic compound, the additive is included in an amount of 0.1 part by weight to 100,000 parts by weight.

12. The resist composition according to claim 1, wherein the solvent includes a polar aprotic solvent.

13. The resist composition according to claim 1, wherein the solvent is selected from a ketone-based solvent, an ester-based solvent, and a combination thereof.

14. The resist composition according to claim 1, wherein the solvent is selected from a linear ketone solvent, a cyclic ketone solvent, an ether carboxylic acid ester solvent containing a polyol, a lactone solvent, an acetate solvent, and a combination thereof.

15. The resist composition according to claim 1, The solvent is selected from methyl ethyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, n-butyl acetate, and combinations thereof.

16. The resist composition according to claim 1, wherein... The resist composition is substantially free of photoacid-producing agents.

17. A method for forming a pattern, the method comprising: Apply the resist composition according to any one of claims 1 to 16 to form a resist film; At least a portion of the resist film is exposed to high-energy radiation to provide the exposed resist film; as well as The exposed resist film is developed using a developer.

18. The method according to claim 1, The exposure of at least a portion of the resist film is performed by irradiation with at least one of deep ultraviolet (DUV), extreme ultraviolet (EUV), or electron beam (EB).

19. The method according to claim 17, The organometallic compound decomposes by exposing at least a portion of the resist film.

20. The method according to claim 17, The exposed resist film includes exposed and non-exposed portions, and in, During the development of the exposed resist film, the exposed portion is removed.

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