Resist composition and pattern forming method using same

Abstract

A resist composition and a pattern forming method using the same are provided. The resist composition may include an organometallic compound represented by one of Formulae 1-1 to 1-4 and an additive represented by Formula 2, wherein 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 are described in the specification. # imgabs 0 # formula 2 # imgabs 1 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on and claims the benefit of priority from Korean Patent Application No. 10-2023-0151944 filed on November 6, 2023 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference. Technical Field

[0003] The present disclosure relates to a resist composition and a pattern forming method using the same. Technical Field

[0005] During the manufacture of semiconductors, resists whose physical properties change in response to light are being used to form fine patterns. Among these resists, chemically amplified resists have been widely used. In the case of chemically amplified resists, an acid formed by a reaction between light and a photoacid generator reacts again with a base resin to change the solubility of the base resin in a developer, thereby enabling patterning.

[0006] However, in the case of chemically amplified resists, diffusion of the formed acid into unexposed areas can lead to poor pattern uniformity and increased surface roughness. With increasingly miniaturized semiconductor processes, it is not easy to control the diffusion of the acid, resulting in the need to develop new types of resists.

[0007] Recently, efforts have been made to develop materials whose physical properties change as a result of exposure to light in order to overcome the limitations of chemically amplified resists. However, the dose required for exposure is still high. Summary of the invention

[0008] Provided are a resist composition having improved storage stability, the properties of which are changed even at a low exposure dose, and which provides a pattern with improved resolution, and a pattern forming method using the same.

[0009] Additional 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 presented embodiments of the disclosure.

[0010] According to example embodiments, the resist composition may include an organic metal compound represented by one of Formulae 1-1 to 1-4 and an additive represented by Formula 2.

[0011]

[0012] Formula 2

[0013]

[0014] In Formulas 1-1 to 1-4 and 2,

[0015] M 11 It may be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po),

[0016] L 11 To L 14 may be each independently a single bond or a substituted or unsubstituted linear, branched or cyclic C optionally including heteroatoms 1 -C 30 Divalent hydrocarbon groups,

[0017] a11 to a14 may each independently be an integer of 1 to 4, and

[0018] R 11 To R 14 may be independently substituted or unsubstituted C 3 -C 30 Branched alkyl, substituted or unsubstituted C 3 -C 30 Cycloalkyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl, substituted or unsubstituted C 2 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Cycloalkenyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl, substituted or unsubstituted C 2 -C 30 Alkynyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 7 -C 30 Arylalkyl, substituted or unsubstituted C 1 -C 30 heteroaryl, or substituted or unsubstituted C 2 -C 30 Heteroarylalkyl,

[0019] R 11 To R 14 Adjacent two of may optionally be combined with each other to form a ring (eg, a fused ring (fused ring)),

[0020] b11 to b14 may each independently be an integer from 1 to 4,

[0021] Y 11 To Y 13 can be independently O, OC (= O), S, SC (= O), NX 14, or NX 14 C(=O), and

[0022] X 11 To X 14 may be each independently hydrogen, deuterium, or a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0023] Y 21 and Y 22 Each of them may be independently a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0024] L 21 It may be a single bond, a double bond, or a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0025] a21 may be an integer from 1 to 4, and

[0026] Y 21 , Y 22 , and L 21 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0027] According to example embodiments, a pattern forming method may include forming a resist film by applying the resist composition on a substrate, exposing at least a portion of the resist film to high-energy rays to provide an exposed resist film, and developing the exposed resist film using a developer. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The above and other aspects, features, and advantages of some embodiments will become more apparent from the following description considered in conjunction with the accompanying drawings, in which:

[0029] Figure 1 is a flow chart showing a pattern forming method according to an embodiment;

[0030] FIG. 2A to FIG. 2C is a side cross-sectional view showing a pattern forming method according to an embodiment;

[0031] Figure 3A is a graph showing changes in film thickness after development depending on the dose of Comparative Example 3-1;

[0032] Figure 3Bis a graph showing changes in film thickness after development depending on the dose of Example 3-1;

[0033] Figures 4A to 4E is a side cross-sectional view illustrating a method of forming a patterned structure according to an embodiment; and

[0034] Figures 5A to 5E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment. DETAILED DESCRIPTION

[0035] Embodiments will now be described in detail, and examples thereof are illustrated in the accompanying drawings, wherein the same reference numerals always refer to the same elements. In this regard, the present embodiment may have different forms and should not be construed as being limited to the description set forth herein. Therefore, embodiments are described below with reference to the accompanying drawings to illustrate aspects of the present specification. As used herein, the term "and / or" includes any and all combinations of one or more of the related enumerated items. Statements such as "at least one (kind) of ... ", when before or after the list of elements, modify the entire list of elements and do not modify the individual elements of the list. For example, "at least one (kind) of A, B, and C" and similar language (e.g., "selected from at least one (kind) of A, B, and C", "at least one (kind) of A, B, or C") can be interpreted as only A, only B, only C, or any combination of two (kinds) or more (kinds) of A, B, and C, such as ABC, AB, BC, and AC.

[0036] When the terms "about" or "substantially" are used in this specification with respect to a numerical value, it is intended that the associated numerical value includes a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value. In addition, when the words "substantially" and "substantially" are used with respect to a geometric shape, it is intended that the accuracy of the geometric shape is not required, but that tolerances for the shape are within the scope of the present disclosure. In addition, regardless of whether a numerical value or shape is modified with "about" or "substantially", it will be understood that these values ​​and shapes should be interpreted as including a manufacturing or operating tolerance (e.g., ±10%) around the stated numerical value or shape.

[0037] Since the present disclosure can be applied to a variety of transformations and has a variety of embodiments, specific embodiments will be shown in the drawings and described in detail in the specific embodiments. However, it should be understood that this is not intended to limit the present disclosure to specific embodiments, but to include all transformations, equivalents and substitutes included in the spirit and scope of the present disclosure. When describing the present disclosure, when it is determined that the specific description of known related art unnecessarily obscures the subject matter of the present disclosure, its detailed description will be omitted.

[0038] It will be understood that although the terms "first", "second", and "third" may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element, and are not used to limit the order or type of the elements.

[0039] In this specification, when a part of a layer, film, region, plate, etc. is described as being "on" or "over" another part, it may include not only the meaning of "directly on / below / left / right of..." in a contacting manner, but also the meaning of "on / below / left / right of..." in a non-contacting manner.

[0040] Expressions used in the singular encompass expressions in the plural, unless they have clearly different meanings in the context. Hereinafter, unless explicitly described to the contrary, it will be understood that terms such as "include", "have", and "comprise" are intended to indicate the presence of features, numbers, steps, actions, components (parts), parts, ingredients, materials, or combinations thereof disclosed in this specification, and are not intended to exclude the possibility that one or more other features, numbers, steps, actions, components (parts), parts, ingredients, materials, or combinations thereof may exist or may be added.

[0041] Whenever a range of values ​​is listed, the range includes all values ​​falling within the range, as if expressly written, and the range further includes the boundaries of the range. Thus, a range of "X to Y" includes all values ​​between X and Y and also includes X and Y.

[0042] The expression “C x -C y " refers to the case where the number of carbon atoms constituting a group or a substituent is within the range of x to y. For example, the expression "C 1 -C 6 " refers to the case where the number of carbon atoms constituting the group or substituent is within the range of 1 to 6, and the expression "C 6 -C 20 ” refers to the case where the number of carbon atoms constituting the group or substituent is within the range of 6 to 20.

[0043] The term "monovalent hydrocarbon group" as used herein refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples thereof include a straight-chain or branched alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl); a monovalent saturated alicyclic hydrocarbon group (cycloalkyl group) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl); monovalent unsaturated aliphatic hydrocarbon groups (alkenyl or alkynyl) (e.g., allyl); monovalent unsaturated alicyclic hydrocarbon groups (cycloalkenyl) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl, 1-naphthyl, and 2-naphthyl); arylalkyl groups (e.g., benzyl and diphenylmethyl); monovalent hydrocarbon groups containing heteroatoms (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxyl-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl), or combinations thereof. In some embodiments, some of the hydrogens in these groups may be replaced by moieties including heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, or halogen atoms, or some of the carbons in these groups may be replaced by moieties including heteroatoms such as oxygen, sulfur, nitrogen, or phosphorus. Thus, these groups can include cyano groups, nitro groups, hydroxyl groups, thiol groups, amino groups, carboxylate groups, ether moieties, thioether moieties, carbonyl moieties, ester moieties, phosphonate moieties, sulfonate moieties, carbonate moieties, amide moieties, lactone moieties, sultone moieties, carboxylic anhydride moieties, and the like.

[0044] The term "divalent hydrocarbon group" as used herein is a divalent residue and means that any one hydrogen atom of a monovalent hydrocarbon group is replaced by a bonding site with an adjacent atom. The divalent hydrocarbon group may include, for example, a linear or branched alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, a cycloalkenylene group, an arylene group, a group in which some of its carbon atoms are replaced by heteroatoms, and the like.

[0045] As used herein, the term "alkyl" refers to a straight or branched saturated aliphatic monovalent hydrocarbon group, and non-limiting examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl. As used herein, the term "alkylene" refers to a straight or branched saturated aliphatic divalent hydrocarbon group, and non-limiting examples thereof may include methylene, ethylene, propylene, butylene, and isobutylene.

[0046] The term "haloalkyl" as used herein refers to a group in which at least one hydrogen atom of an alkyl group is replaced by a halogen atom, and examples thereof may include CF 3 In this regard, the halogen atom is F, Cl, Br, or I.

[0047] As used herein, the term "alkoxy" refers to a group having the formula -OA 101 A monovalent group, where A 101 Specific examples thereof include methoxy, ethoxy, isopropoxy and the like.

[0048] As used herein, the term "alkylthio" refers to a group having the formula -SA 101 A monovalent group, where A 101 It is an alkyl group.

[0049] The term "haloalkoxy" as used herein refers to a group in which one or more hydrogen atoms of an alkoxy group are replaced by a halogen atom, and specific examples thereof include -OCF 3 wait.

[0050] The term "haloalkylthio group" as used herein refers to a group in which one or more hydrogen atoms of an alkylthio group are replaced by a halogen atom, and specific examples thereof include -SCF 3 wait.

[0051] The term "cycloalkyl" as used herein refers to a monovalent saturated hydrocarbon cyclic group, and specific examples thereof include monocyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and bridged ring groups such as norbornyl and adamantyl. The term "cycloalkylene" as used herein refers to a divalent saturated hydrocarbon cyclic group, and specific examples thereof include cyclopentylene, cyclohexylene, adamantylene, adamantylene methyl, norbornylene, norbornylene methyl, tricyclodecylene, tetracyclododecylene, tetracyclododecylene methyl, dicyclohexylene methyl, etc.

[0052] As used herein, the term "cycloalkoxy" refers to a cycloalkyl group having the formula -OA 102 A monovalent group, where A 102 Specific examples thereof include cyclopropyloxy, cyclobutyloxy and the like.

[0053] As used herein, the term "cycloalkylthio" refers to a group having the formula -SA 102 A monovalent group, where A 102 It is a cycloalkyl group.

[0054] The term "heterocycloalkyl" as used herein may be a group in which some carbon atoms of cycloalkyl are replaced by parts including heteroatoms such as oxygen, sulphur or nitrogen. The heterocycloalkyl may include ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings or carboxylic anhydride moieties. The term "heterocycloalkylene" as used herein refers to a group in which some carbon atoms of cycloalkylene are replaced by parts including heteroatoms such as oxygen, sulphur or nitrogen.

[0055] As used herein, the term "heterocycloalkoxy" refers to a heterocycloalkoxy group having the formula -OA 103 A monovalent group, where A 103 It is a heterocycloalkyl group.

[0056] As used herein, the term "heterocycloalkylthio" refers to a group having the formula -SA 103 A monovalent group, where A 103 It may be a heterocycloalkyl group.

[0057] As used herein, the term "alkenyl" refers to a linear or branched unsaturated aliphatic hydrocarbon monovalent group including one or more carbon-carbon double bonds. As used herein, the term "alkenylene" refers to a linear or branched unsaturated aliphatic hydrocarbon divalent group including one or more carbon-carbon double bonds.

[0058] The term "cycloalkenyl" as used herein refers to a monovalent unsaturated hydrocarbon cyclic group including one or more carbon-carbon double bonds and not having aromaticity. The term "cycloalkenylene" as used herein refers to a divalent unsaturated hydrocarbon cyclic group including one or more carbon-carbon double bonds and not having aromaticity.

[0059] The term "heterocycloalkenyl" as used herein refers to a group in which some of the carbon atoms of a cycloalkenyl group are replaced by a moiety comprising heteroatoms such as oxygen, sulfur, or nitrogen. The term "heterocycloalkenylene" as used herein refers to a group in which some of the carbon atoms of a cycloalkenyl group are replaced by a moiety comprising heteroatoms such as oxygen, sulfur, or nitrogen.

[0060] The term "alkynyl" as used herein refers to a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group including one or more carbon-carbon triple bonds.

[0061] The term "aryl" as used herein refers to a monovalent group having a carbocyclic aromatic system, and non-limiting examples thereof may include phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, and The term "arylene" as used herein refers to a divalent group having a carbocyclic aromatic system.

[0062] As used herein, the term "aryloxy" refers to a 104 A is a monovalent group represented by 104 It is an aromatic group.

[0063] As used herein, the term "arylthio" refers to a 104 A is a monovalent group represented by 104 It is an aromatic group.

[0064] The term "heteroaryl" as used herein refers to a monovalent group having a heterocyclic aromatic system, and specific examples thereof include pyridyl, pyrimidinyl, pyrazinyl, etc. The term "heteroarylene" as used herein refers to a divalent group having a heterocyclic aromatic system.

[0065] As used herein, the term "heteroaryloxy" refers to a 105 A is a monovalent group represented by 105 It is a heteroaryl group.

[0066] As used herein, the term "heteroarylthio" refers to a 105 A is a monovalent group represented by 105 It is a heteroaryl group.

[0067] The term "arylalkyl" as used herein refers to a group in which an alkyl group is substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include benzyl, diphenylmethyl and the like.

[0068] The term "heteroarylalkyl" as used herein refers to a group in which an alkyl group is substituted with a monovalent group having a heterocyclic aromatic system.

[0069] The term "heterocyclic group" as used herein refers to a monocyclic or polycyclic group having 1 to 60 carbon atoms including at least one heteroatom, and includes a monovalent group, a divalent group, and a trivalent group.

[0070] The term "substituent" as used herein includes deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate group, an ether moiety, a thioether moiety, a carbonyl moiety, an ester moiety, a phosphonate moiety, a sulfonate moiety, a carbonate moiety, an amide moiety, a lactone moiety, a sultone moiety, a carboxylic anhydride moiety, a C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, or C 1 -C 20 heteroarylthio;

[0071] Each of C is substituted by 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, and C 1 -C 20 Heteroarylthio group: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1-C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryl, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof; and

[0072] Its combination.

[0073] As used herein, the expression "C 1 -C 30 ”, “C 2 -C 30 ”, “C 3 -C 30 ”, “C 6 -C 30 ” and “C 7 -C 30 "The upper limit C 30 Preferably, it can be changed to C 20 , C 14 , C 13 , C 12 , C 11 , C 10 , C 9 , C 8 or C 6 , and the expression "C 1 -C 20 ”, “C 3 -C 20 ”, and “C 6 -C 20 "The upper limit C 20 Preferably, it can be changed to C 14 , C 13 , C 12 , C 11 , C 10, C 9 , C 8 or C 6 For example, C 1 -C 30 The alkyl group may preferably be C 3 -C 20 Alkyl, such as C 3 -C 10 Alkyl or C 3 -C 6 Alkyl; C 3 -C 30 The branched alkyl group may preferably be C 3 -C 20 Branched alkyl groups, such as C 3 -C 10 Branched alkyl or C 3 -C 6 Branched alkyl; C 2 -C 30 Alkenyl may preferably be C 2 -C 20 Alkenyl, C 2 -C 10 Alkenyl, or C 2 -C 6 Alkenyl; C 3 -C 30 The cycloalkyl group may preferably be C 3 -C 20 Cycloalkyl, such as C 3 -C 10 Cycloalkyl or C 3 -C 8 Cycloalkyl; C 6 -C 30 Aryl may preferably be C 6 -C 20 Aryl, such as C 6 -C 12 Aryl or C 6 -C 10 Aryl; C 7 -C 30 Arylalkyl may preferably be C 7 -C 20 Arylalkyl, such as C 7 -C 14 Arylalkyl, C 7 -C 12 Arylalkyl, or C 7 -C 10 Arylalkyl; C 1 -C 30 The heteroaryl group may preferably be C 1 -C 20 Heteroaryl, such as C 3 -C10 Heteroaryl or C 5 -C 8 Heteroaryl; and C 2 -C 30 Heteroarylalkyl may preferably be C 2 -C 20 Heteroarylalkyl, such as C 4 -C 11 Heteroarylalkyl or C 6 -C 9 Heteroarylalkyl. Hereinafter, the embodiments will be described in detail with reference to the accompanying drawings, wherein the same reference numerals throughout the drawings represent substantially the same or corresponding components, and redundant descriptions thereof will be omitted. In the drawings, the thicknesses of layers and regions are exaggerated for clarity. In addition, in the drawings, the thicknesses of some layers and regions are exaggerated for ease of description. Meanwhile, the embodiments described herein are merely examples, and various changes may be made therein.

[0074] [Resist composition]

[0075] The resist composition according to the embodiment includes an organic metal compound represented by one of Formulae 1-1 to 1-4 and an additive represented by Formula 2:

[0076]

[0077] Formula 2

[0078]

[0079] Wherein, in Formulas 1-1 to 1-4 and 2,

[0080] M 11 It may be indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po),

[0081] L 11 To L 14 may be each independently a single bond or a substituted or unsubstituted linear, branched or cyclic C optionally including heteroatoms 1 -C 30 Divalent hydrocarbon groups,

[0082] a11 to a14 are each independently an integer of 1 to 4, and

[0083] R 11 To R 14 may be independently substituted or unsubstituted C 3 -C 30 Branched alkyl, substituted or unsubstituted C 3 -C 30Cycloalkyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl, substituted or unsubstituted C 2 -C 30 Alkenyl, substituted or unsubstituted C 3 -C 30 Cycloalkenyl, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl, substituted or unsubstituted C 2 -C 30 Alkynyl, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 7 -C 30 Arylalkyl, substituted or unsubstituted C 1 -C 30 heteroaryl, or substituted or unsubstituted C 2 -C 30 Heteroarylalkyl,

[0084] R 11 To R 14 Adjacent two of may optionally be bonded to each other to form a ring (eg, a fused ring),

[0085] b11 to b14 may each independently be an integer from 1 to 4,

[0086] Y 11 To Y 13 can be independently O, OC (= O), S, SC (= O), NX 14 , or NX 14 C(=O), and

[0087] X 11 To X 14 may be each independently hydrogen, deuterium, or a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0088] Y 21 and Y 22 Each of them may be independently a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0089] L 21 It may be a single bond, a double bond, or a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Divalent hydrocarbon groups,

[0090] a21 may be an integer from 1 to 4, and

[0091] Y 21 , Y 22 and L 21 Two adjacent ones of may optionally be bonded to each other to form a fused ring,

[0092] The molecular weight of the organometallic compound may be 3000 g / mol or less. In an embodiment, the molecular weight of the organometallic compound may be 2000 g / mol or less.

[0093] While not limited to any particular theory, the organometallic compound may be capable of forming free radicals through heat and / or high energy radiation. In an embodiment, the free radicals may be formed by M of the organometallic compound. 11 -carbon bond formation, and optionally in an atmosphere in which water is present, the free radicals can react to form chemical bonds between the organometallic compounds. As a result, the physical properties of the organometallic compound, such as its solubility in the developer, can be changed.

[0094] The organometallic compound represented by one of Formulae 1-1 to 1-4 must include R having a relatively low CH bond decomposition energy. 11 To R 14 Therefore, its photosensitivity to high-energy rays such as extreme ultraviolet (EUV) rays can be improved. In particular, R in the organic metal compound represented by one of Formulae 1-1 to 1-4 11 To R 14 It cannot be a straight-chain alkyl group. In the case of a straight-chain alkyl group, the free radical formed by the equilibrium homolysis of the CH bond is relatively unstable, and therefore, the CH bond decomposition energy is relatively high. Therefore, a straight-chain alkyl group is not suitable for R 11 To R 14 .

[0095] For example, M in Formulas 1-1 to 1-4 11 In, Sn, or Sb. In the embodiment, M in Formulas 1-1 to 1-4 11 It can be Sn.

[0096] In some embodiments, L in Formulas 1-1 to 1-4 11 To L 14 can be independently a single bond, a substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 3 -C 30 Cycloalkylene, substituted or unsubstituted C 3 -C 30Heterocycloalkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 3 -C 30 Cycloalkenylene, substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene, substituted or unsubstituted C 6 -C 30 Arylene, or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0097] In some embodiments, L in Formulas 1-1 to 1-4 11 To L 14 may each independently be: a single bond; and C each being unsubstituted or substituted as follows 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Heterocycloalkylene, C 2 -C 30 Alkenylene, C 3 -C 30 Cycloalkenylene, C 3 -C 30 Heterocycloalkenylene, C 6 -C 30 Arylene, and C 1 -C 30 Heteroarylene group: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0098] In some embodiments, L in Formulas 1-1 to 1-4 11 To L 14 may be independently: a single bond; and C 1 -C 30 Alkylene: deuterium, halogen atoms, hydroxyl, cyano, C 1 -C 20 Alkyl, C 1 -C 20 haloalkyl, or a combination thereof.

[0099] For example, a11 to a14 in Formulae 1-1 to 1-4 may each independently be an integer of 1 or 2.

[0100] In some embodiments, R in Formulas 1-1 to 1-4 11 To R 14 can be independently selected from: branched C 3 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Heterocycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0101] In some embodiments, R in Formulas 1-1 to 1-4 11 To R 14 can be independently selected from branched C 3 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, and C 7 -C 30Arylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0102] In some embodiments, R in Formulas 1-1 to 1-4 11 To R 14 Each independently can be one of formulas 3-1 to 3-15:

[0103]

[0104] Among them, in formulas 3-1 to 3-15,

[0105] At least one hydrogen may be optionally replaced by deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C1 -C 20 It can be replaced by a haloalkylthio group, or a combination thereof.

[0106] b11 to b14 in Formulas 1-1 to 1-4 respectively refer to substituents R 11 The number of substituents R 14 For example, b11 to b14 in Formulae 1-1 to 1-4 may each independently be 1 or 2.

[0107] R 11 To R 14 Adjacent two of may optionally be bonded to each other to form a ring (eg, a fused ring).

[0108] For example, multiple R 11 Two adjacent R may optionally be combined with each other to form a ring (eg, a fused ring), and multiple R 12 Two adjacent R may optionally be combined with each other to form a ring (eg, a fused ring), and multiple R 13 Adjacent two of may optionally be combined with each other to form a ring (eg, a fused ring), and a plurality of R 14 Adjacent two of may optionally be bonded to each other to form a ring (eg, a fused ring).

[0109] Y 11 To Y 13 can be independently O, OC (= O), S, SC (= O), NX 14 , or NX 14 C(=O).

[0110] For example, Y in Formulas 1-1 to 1-4 11 To Y 13 They may each independently be O, OC(═O), S, or SC(═O).

[0111] For example, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 1 -C 30 Alkoxy, C 1 -C 30 Alkylthio, C 1 -C 30 Halogenated alkoxy, C 1 -C 30 Halogenated alkylthio, C 3 -C 30 Cycloalkyl, C3 -C 30 Cycloalkoxy, C 3 -C 30 Cycloalkylthio, C 3 -C 30 Heterocycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 6 -C 30 Aryloxy, C 6 -C 30 Arylthio, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, C 1 -C 30 Heteroaryloxy, C 1 -C 30 Heteroarylthio, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6-C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0112] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 aryl, or a combination thereof.

[0113] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 may be independently selected from: hydrogen; deuterium; and C 1 -C 30 Alkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C2 -C 30 Alkynyl, and C 6 -C 30 Aryl: deuterium, a halogen atom, or a combination thereof.

[0114] In some embodiments, X in Formulas 1-1 to 1-4 11 To X 14 Each independently may be: 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, each of which is unsubstituted or substituted with: deuterium, a halogen atom, methyl, ethyl, phenyl, naphthyl, or a combination thereof.

[0115] In an embodiment, the organometallic compound represented by one of Formulae 1-1 to 1-4 may be selected from Group I:

[0116] Group I

[0117]

[0118]

[0119] Wherein n in group I is an integer from 1 to 4.

[0120] For example, n in group I may be 2.

[0121] For example, Y in Formula 2 21 It can be represented by one of the formulas 4-1 to 4-5, and Y 22 It can be expressed by one of the formulas 4-6 to 4-10:

[0122]

[0123] Among them, in formulas 4-1 to 4-10,

[0124] X 41 and X 44 can be N or P independently,

[0125] X 42 and X 45 can be independently O or S,

[0126] X 43 and X 46 can be independently O, S, N, or P,

[0127] Y in formula 4-3 and 4-8 41 and Y 42 Can be C or S independently, Y in formula 4-4 and 4-9 41 and Y42 Each is P,

[0128] A 41 Can include X 43 C as a ring member 1 -C 30 Heterocyclic groups,

[0129] A 42 Can include X 46 C as a ring member 1 -C 30 Heterocyclic groups,

[0130] R 41 To R 44 may be each independently hydrogen, deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate group, or a substituted or unsubstituted linear, branched or cyclic C 1 -C 30 Monovalent hydrocarbon groups,

[0131] b41 and b42 may each independently be an integer from 1 to 10, and

[0132] *Indicates the binding site with the adjacent atom.

[0133] In an embodiment, X in the additive 41 To X 43 One and X 44 To X 46 One of them may be combined with the metal atom M in the organometallic compound represented by one of Formulae 1-1 to 1-4. 11 Coordinate to form a five-membered, six-membered, or seven-membered ring structure. By using the combination of the organic metal compound and the additive, the resist composition can have improved storage stability and coating characteristics while having high photosensitivity to high-energy rays such as extreme ultraviolet (EUV) rays.

[0134] For example, A in Formula 4-5 and Formula 4-10 41 and A 42 may each independently be 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 to each other, or iii) a monovalent group derived from a fused ring in which one or more first rings are fused to one or more second rings,

[0135] The first ring can be 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

[0136] The second ring may be cyclopentane, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, or naphthalene.

[0137] For example, A in Formula 4-5 and Formula 4-10 41 and A 42 may each independently be 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 to each other, or iii) a monovalent group derived from a fused ring in which one or more first rings are fused to one or more second rings,

[0138] The first ring can be 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

[0139] The second ring may be benzene.

[0140] For example, R in Formulas 4-1 to 4-10 41 To R 44 may be independently selected from: hydrogen; deuterium; halogen atoms; cyano groups; nitro groups; hydroxyl groups; thiol groups; amino groups; carboxylate groups; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 3 -C 30 Cycloalkyl, C 3 -C 30 Heterocycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C 7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0141] In some embodiments, R in Formulas 4-1 to 4-10 41 To R 44 may be independently selected from: hydrogen; deuterium; halogen atoms; cyano groups; nitro groups; hydroxyl groups; thiol groups; amino groups; carboxylate groups; and C 1 -C 30 Alkyl, C 1 -C 30 Haloalkyl, C 3 -C 30 Cycloalkyl, C 2 -C 30 Alkenyl, C 3 -C 30 Cycloalkenyl, C 3 -C 30 Heterocycloalkenyl, C 2 -C 30 Alkynyl, C 6 -C 30 Aryl, C7 -C 30 Arylalkyl, C 1 -C 30 Heteroaryl, and C 2 -C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 aryl, or a combination thereof.

[0142] In an embodiment, in Formula 2, i) Y 21 It is represented by formula 4-5, and Y 22 is represented by one of Formulas 4-6 to 4-10, or

[0143] ii) Y 21 It can be represented by one of the formulas 4-1 to 4-5, and Y 22 It can be expressed by formula 4-10.

[0144] In an embodiment, in Formula 2, Y 21 It can be expressed by formula 4-5, and Y 22 It can be expressed by formula 4-10.

[0145] In some embodiments, L in Formula 2 21 Can be single bond, double bond, substituted or unsubstituted C 1 -C 30 Alkylene, substituted or unsubstituted C 3 -C 30 Cycloalkylene, substituted or unsubstituted C 3 -C 30 Heterocycloalkylene, substituted or unsubstituted C 2 -C 30 Alkenylene, substituted or unsubstituted C 3 -C 30 Cycloalkenylene, substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene, substituted or unsubstituted C 6 -C 30 Arylene, or substituted or unsubstituted C 1 -C 30 Heteroarylene.

[0146] In some embodiments, L in Formula 221 can be selected from: a single bond; a double bond; and C each being unsubstituted or substituted as follows 1 -C 30 Alkylene, C 3 -C 30 Cycloalkylene, C 3 -C 30 Heterocycloalkylene, C 2 -C 30 Alkenylene, C 3 -C 30 Cycloalkenylene, C 3 -C 30 Heterocycloalkenylene, C 6 -C 30 Arylene, and C 1 -C 30 Heteroarylene group: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C 1 -C 20 Alkyl, C 1 -C 20 Haloalkyl, C 1 -C 20 Alkoxy, C 1 -C 20 Alkylthio, C 1 -C 20 Halogenated alkoxy, C 1 -C 20 Halogenated alkylthio, C 3 -C 20 Cycloalkyl, C 3 -C 20 Cycloalkoxy, C 3 -C 20 Cycloalkylthio, C 6 -C 20 Aryl, C 1 -C 20 Heteroaryl, C 6 -C 20 Aryloxy, C 6 -C 20 Arylthio, C 1 -C 20 Heteroaryloxy, C 1 -C 20 heteroarylthio, or a combination thereof.

[0147] In some embodiments, L in Formula 2 21 can be selected from: a single bond; a double bond; and C each being unsubstituted or substituted as follows 1 -C30 Alkylene and C 2 -C 30 Alkenylene: deuterium, halogen atoms, hydroxyl, cyano, C 1 -C 20 Alkyl, C 1 -C 20 haloalkyl, or a combination thereof.

[0148] In an embodiment, the additive may be represented by Formula 2-1:

[0149]

[0150] In formula 2-1,

[0151] X 43 , X 46 , A 41 , A 42 , L 21 、a21、R 41 , R 43 , b41, and b42 may be the same as described above.

[0152] In an embodiment, the additive may be represented by Formula 2-11 or Formula 2-12:

[0153]

[0154] Among them, in formulas 2-11 and 2-12,

[0155] X 43 and X 46 can be independently O, S, N, or P,

[0156] A 41 Can include X 43 C as a ring member 1 -C 30 Heterocyclic groups,

[0157] A 42 Can include X 46 C as a ring member 1 -C 30 Heterocyclic groups,

[0158] Z 21 and Z 22 can be independently C or N,

[0159] In Z 21 and Z 22 The bond between can be a single bond or a double bond,

[0160] L 22can be a single bond; a double bond; and each C is unsubstituted or substituted as follows 1 -C 30 Alkylene and C 2 -C 30 Alkenylene: deuterium, halogen atoms, hydroxyl, cyano, C 1 -C 20 Alkyl, C 1 -C 20 haloalkyl, or a combination thereof,

[0161] a22 can be an integer from 1 to 4,

[0162] R 41 and R 43 may be independently substituted or unsubstituted, optionally containing heteroatoms, linear, branched or cyclic C 1 -C 30 a monovalent hydrocarbon group, and

[0163] b41 and b42 may each independently be an integer of 1 to 10 (eg, 1 to 4).

[0164] In equations 2-11 and 2-12, 43 and Z 21 The key between Z 22 and X 46 The bonds between can each independently be single bonds or double bonds.

[0165] For example, in equations 2-11 and 2-12, in X 43 and X 46 There may be three chemical bonds between X and 43 and Z 21 The chemical bonds between 21 and Z 22 The chemical bonds between 22 and X 46 The chemical bonds between.

[0166] In an embodiment, the additive may be selected from Group II:

[0167] Group II

[0168]

[0169]

[0170] Since the additive contains N, O, S, and / or P which provide a lone pair of electrons, it can form a coordination bond with the organometallic compound, thereby improving the (eg, chemical) stability of the organometallic compound.

[0171] The organometallic compound may be one type of Formulae 1-1 to 1-4, or a mixture of two or more types thereof.

[0172] Likewise, the additive may be one type represented by Formula 2, or a mixture of two or more types thereof.

[0173] The amount of the organometallic compound in the resist composition may be about 0.01 parts by weight to about 100 parts by weight, such as 0.2 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more, and 90 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less, based on 100 parts by weight of the resist composition. Within these ranges, chemical bonds between the organometallic compounds are sufficiently formed while side reactions are suppressed, thereby providing a resist composition with improved sensitivity (sensitivity) and / or resolution.

[0174] The amount of the additive in the resist composition may be, based on 100 parts by weight of the resist composition, from about 0.01 parts by weight to about 100 parts by weight, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.5 parts by weight or more, 1 parts by weight or more, or 1.5 parts by weight or more, and 90 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1.5 parts by weight or less. Within these ranges, chemical bonds between the organometallic compounds are sufficiently formed while side reactions are suppressed, thereby providing a resist composition with improved sensitivity and / or resolution.

[0175] The amount of the additive in the resist composition may be from about 0.1 parts by weight to about 100,000 parts by weight, based on 100 parts by weight of the organometallic compound. In some embodiments, based on 100 parts by weight of the organometallic compound, the additive may be included in an amount of from about 5 parts by weight to about 1,000 parts by weight, for example, from about 7 parts by weight to about 1,000 parts by weight, from about 10 parts by weight to about 1,000 parts by weight, for example, from about 20 parts by weight to about 100 parts by weight, from about 30 parts by weight to about 80 parts by weight, or from about 40 parts by weight to about 60 parts by weight. Within these ranges, the storage stability of the resist composition can be significantly improved, while the photoresponsivity of the resist composition to which the additive is added is maintained at a high level.

[0176] The solubility of the resist composition in the developer can be changed by exposure to high-energy rays. The resist composition can be a negative resist composition in which the unexposed part of the resist film is dissolved and removed to form a negative resist pattern, or a positive resist composition in which the exposed part is dissolved and removed to form a positive resist pattern. The resist composition can be adjusted in many ways. For example, depending on the type of exposure intensity and / or developer, the resist composition can be negative or positive.

[0177] In addition, when forming a resist pattern, the resist composition according to the embodiment can be used for: an alkaline development process using an alkaline developer for development treatment; or a solvent development process using a developer containing an organic solvent (hereinafter, also referred to as an organic developer) for development treatment.

[0178] The resist composition may be non-chemically amplified, in which case, it may substantially exclude a photoacid generator.

[0179] Since physical properties of the organometallic compound are changed by exposure, the resist composition may substantially exclude a compound having a molecular weight of 1,000 g / mol or more other than the organometallic compound.

[0180] The organometallic compound and the additive may be manufactured by any appropriate method, or commercially available products may be used therefor.

[0181] The structure (composition) of the organometallic compound can be determined by 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. The detailed confirmation method is described in the following examples.

[0182] <Organic Solvents>

[0183] The resist composition may further include an organic solvent.

[0184] The organic solvent included in the resist composition is not particularly limited as long as the organometallic compound, the additive, and any component contained therein as needed are dissolved or dispersed therein. As the organic solvent, one type of organic solvent may be used, or two or more different types of organic solvents may be used in combination.

[0185] In an embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or a combination thereof.

[0186] In some embodiments, the organic solvent may be a mixture including an aprotic organic solvent and a protic organic solvent.

[0187] Since the resist composition may not substantially include water, the organic solvent may not include water. In an embodiment, the resist composition may include no more than 3 wt % of water, and the organic solvent may include no more than 3 wt % of water.

[0188] Examples of the organic solvent are alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, hydrocarbon-based solvents, and the like.

[0189] Examples of the alcohol-based solvent may include monohydric alcohol-based solvents 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-ethylpentanol, Butanol, 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-undecyl alcohol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.; polyol solvents, such as ethylene glycol, 1,2-propylene glycol , 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 containing polyols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, Ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl 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, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, etc.

[0190] Examples of the ether-based solvent may include: diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether; dialkyl ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, etc.; cyclic ether-based solvents such as tetrahydrofuran, tetrahydropyran, etc.; and aromatic ring-containing ether-based solvents such as diphenyl ether, anisole, etc.

[0191] Examples of the ketone-based solvent are chain ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, or trimethylnonanone, and cyclic ketone-based solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, and acetophenone.

[0192] Examples of the amide-based solvent are cyclic amide-based solvents such as N,N'-dimethylimidazolidinone or N-methyl-2-pyrrolidone, and chain amide-based solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, or N-methylpropionamide.

[0193] Examples of the ester-based solvent are: acetate-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-amyl acetate, isoamyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, and n-nonyl acetate; polyol-containing ether carboxylic acid ester-based solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate (PGMA) The present invention relates to solvents based on dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; solvents based on lactate, such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; ethylene glycol diacetate, methoxydiglycol 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.

[0194] Examples of the sulfoxide-based solvent are dimethyl sulfoxide and diethyl sulfoxide.

[0195] Examples of the hydrocarbon-based solvent are aliphatic hydrocarbon-based solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, or isooctane; alicyclic hydrocarbon-based solvents such as cyclohexane, or methylcyclohexane; and aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, or n-pentylnaphthalene.

[0196] In some embodiments, the organic solvent may be selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, and any combination thereof. In some embodiments, the organic solvent may be selected from 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and combinations thereof.

[0197] The organic solvent may be used in an amount of about 0 parts by weight to about 99.9 parts by weight based on 100 parts by weight of the resist composition. The organic solvent may be used alone, or any mixture of two or more different organic solvents may also be used.

[0198] <Other components>

[0199] If necessary, the resist composition may further include a surfactant, a crosslinking agent, a leveling agent, a colorant, or a combination thereof.

[0200] The resist composition may further include a surfactant to improve coating properties, developability, etc. The example of the surfactant is a nonionic surfactant such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate. As the surfactant, commercially available products or synthetic products can be used. Examples of commercially available products of the surfactant are KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.75 and Polyflow No.95 (manufactured by Kyoeisha Chemical Co., LTD.), Eftop EF301, Eftop 303, and Eftop 352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE TM F171、MEGAFACE TMF173, R-40, R-41, and R-43 (products manufactured by DIC Corporation), Fluorad TM FC430 and Fluorad TM FC431 (manufactured by Sumitomo 3M, Ltd.), Asahi Guard TM AG710 (manufactured by AGC Seimi Chemical Co., Ltd.), and Surflon TM S-382, Surflon TM SC-101, Surflon TM SC-102, Surflon TM SC-103, Surflon TM SC-104, Surflon TM SC-105, and Surflon TM SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0201] The surfactant may be included in an amount ranging from about 0 parts by weight to about 20 parts by weight based on 100 parts by weight of the resist composition. As the surfactant, one type of surfactant may be used, or two or more different types of surfactants may be mixed and used.

[0202] The method for preparing the resist composition is not particularly limited, and the resist composition can be prepared by, for example, mixing the organometallic compound, the additive, and the optional components added when necessary. The temperature or time during mixing is not particularly limited. If necessary, filtering can be performed after mixing.

[0203] [Pattern Formation Method]

[0204] In the following, reference will be made to Figure 1 and 2A 2C describe the pattern forming method according to the embodiment in more detail. Figure 1 is a flowchart representing a pattern forming method according to an embodiment, and Figures 2A to 2C Each is a side cross-sectional view illustrating a pattern forming method according to an embodiment. Hereinafter, a pattern forming method using a negative resist composition will be described as an example, but the embodiment is not limited thereto.

[0205] Reference Figure 1, the pattern forming method may include: an operation S101 of applying a resist composition to form a resist film, an operation S102 of exposing at least a portion of the resist film to high-energy rays to provide an exposed resist film, and an operation S103 of developing the exposed resist film using a developer. First, a substrate 100 may be prepared. The substrate 100 may include, 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 a III-V compound such as GaP, GaAs, GaSb, etc.

[0206] The resist composition can be applied to the substrate 100 to a desired thickness by, for example, coating to form a resist film 110. If necessary, the resist film 110 can be heated (pre-baked, PB) to remove the organic solvent remaining therein. In some embodiments, by heating the resist film 110, free radicals can be generated, and then by exposure, the free radicals can be chemically combined to form crosslinks.

[0207] As coating method, spin coating, dipping, roller coating or other common coating methods can be used. In these coating methods, in particular, spin coating can be used, and the viscosity, concentration and / or rotation speed of the resist composition can be adjusted to form a resist film 110 with a desired thickness. In some embodiments, the resist film 110 can have a thickness of about 10nm to about 300nm. In some embodiments, the resist film 110 can have a thickness of about 30nm to about 200nm.

[0208] The lower limit of the temperature of PB may be 60° C. or higher, or 80° C. or higher. In some embodiments, the upper limit of the temperature of PB may be 150° C. or lower, or 140° C. or lower. The lower limit of the time of PB may be 5 seconds or more, or 10 seconds or more. The upper limit of the time of PB may be 600 seconds or less, or 300 seconds or less.

[0209] Before the resist composition is applied to the substrate 100, an etching target film (not shown) may be further formed on the substrate 100. The etching target film may refer to a layer to which an image is transferred from a resist pattern and transformed into a certain pattern. In an embodiment, the etching target film may be formed to include, for example, an insulating material such as silicon oxide, silicon nitride, and silicon oxynitride. In some embodiments, the etching target film may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicon nitride. In some embodiments, the etching target film may be formed to include a semiconductor material such as polysilicon.

[0210] In an embodiment, an anti-reflection film may be further formed on the substrate 100 to maximize the efficiency of the resist. The anti-reflection film may be an organic or inorganic anti-reflection film.

[0211] In an embodiment, a protective film may be further provided on the resist film 110 to reduce the influence of alkaline impurities etc. included during the process. When immersion exposure is performed, for example, a protective film for immersion may also be formed on the resist film 110 to avoid direct contact between the immersion medium and the resist film 110.

[0212] Next, at least a portion of the resist film 110 may be exposed to high energy rays. For example, high energy rays may be irradiated onto at least a portion of the resist film 110 through the mask 120. For this reason, the resist film 110 may have an exposed portion 111 and an unexposed portion 112.

[0213] Although not limited to a particular theory, free radicals are generated in the exposed portion 111 by exposure, and chemical bonds are formed between the free radicals, which may change the physical properties of the resist composition.

[0214] In some cases, exposure can be performed by irradiating high-energy rays through a mask having a certain pattern using a liquid such as water as a medium. Examples of the high-energy rays may include electromagnetic waves such as ultraviolet rays, deep ultraviolet rays, extreme ultraviolet (EUV) rays (wavelength of 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams (EB) and alpha particle beams. Irradiation with high-energy rays may be collectively referred to as "exposure".

[0215] A variety of light sources can be used for exposure. For example, a light source emitting a laser beam in the UV range, such as a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), and a F 2 Excimer laser (wavelength of 157 nm), a light source (YAG or semiconductor laser) that emits a harmonic laser beam in the far ultraviolet or vacuum ultraviolet range by converting the wavelength of a laser beam received from a solid laser light source, and a light source that emits EB or EUV. During exposure, exposure can usually be performed through a mask corresponding to a desired pattern, but when the exposure light is EB, exposure can be performed by direct writing without using a mask.

[0216] When extreme ultraviolet rays are used as high-energy rays, the integrated dose of the high-energy rays may be 2000 mJ / cm 2 or less, or 500mJ / cm 2 Or less. In addition, when EB is used as high-energy ray, the integrated dose can be 5000μC / cm 2 or less, or 1000μC / cm 2 or less.

[0217] In addition, a post-exposure bake (PEB) may be performed after exposure. The lower limit of the temperature of the PEB may be 50° C. or higher, or 80° C. or higher. The upper limit of the temperature of the PEB may be 250° C. or lower, or 200° C. or lower. The lower limit of the time of the PEB may be 5 seconds or more, or 10 seconds or more. The upper limit of the time of the PEB may be 600 seconds or less, or 300 seconds or less.

[0218] Next, the exposed resist film 110 may be developed using a developer. The unexposed region 112 may be removed by being washed away by the developer, and the exposed portion 111 remains without being washed away by the developer.

[0219] Examples of the developer are alkaline developers and developers including organic solvents (hereinafter also referred to as "organic developers"). Examples of the developing method are dipping, puddle, spray, dynamic injection, etc. The developing temperature may be, for example, 5° C. or more and 60° C. or less, and the developing time may be, for example, 5 seconds or more and 300 seconds or less.

[0220] 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, methyldiethylamine, ethyldimethylamine, 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.

[0221] The lower limit of the amount of the alkaline compound contained in the alkaline developer may be 0.1 wt % or more, or 0.5 wt % or more, or 1 wt % or more. In an embodiment, the upper limit of the amount of the alkaline compound contained in the alkaline developer may be 20 wt % or less, or 10 wt % or less, or 5 wt % or less.

[0222] Examples of the organic solvent included in the organic developer may include the same organic solvents as those exemplified in the <Organic Solvent> section of [Resist Composition]. In an embodiment, the organic developer may include or be n-butyl acetate (nBA), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), isopropyl alcohol (IPA), etc. The organic developer may further include an organic acid such as acetic acid, formic acid, citric acid, etc.

[0223] Regarding the organic developer, the lower limit of the amount of the organic solvent may be 80 wt % or more, 90 wt % or more, 95 wt % or more, or 99 wt % or more.

[0224] The organic developer may further include a surfactant. In addition, the organic developer may include a trace amount of water. In some embodiments, during development, development may be stopped by replacing the organic developer with a solvent of a different type than the organic developer.

[0225] The resist pattern after development may be further cleaned. Ultrapure water, a cleaning solution, etc. may be used as a cleaning solution. The cleaning solution is not particularly limited as long as the cleaning solution does not dissolve the resist pattern, and a solution including a common organic solvent may be used. For example, the cleaning solution may be an alcohol-based solvent or an ester-based solvent. After cleaning, the cleaning solution remaining on the substrate 100 and the resist pattern may be removed. In addition, when ultrapure water is used, water remaining on the substrate 100 and the resist pattern may be removed.

[0226] Furthermore, the developers may be used alone or in combination of two or more.

[0227] After forming the resist pattern as described above, a pattern interconnect substrate can be obtained by etching. The etching can be performed by a known method including dry etching using plasma gas and wet etching using an alkaline solution, a copper (II) chloride solution, an iron (II) chloride solution, and the like.

[0228] After the resist pattern is formed, plating may be performed. The plating is not particularly limited, and examples thereof may include copper plating, solder plating, nickel plating, gold plating, and the like.

[0229] The resist pattern remaining after etching can be stripped with an organic solvent. One or more embodiments are not limited thereto, but examples of such organic solvents may include PGMEA, PGME, ethyl lactate (EL), etc. The stripping method is not particularly limited, but examples thereof may include immersion, spraying, etc. In addition, the interconnect substrate on which the resist pattern is formed may be a multilayer interconnect substrate or may have a small diameter through hole.

[0230] In an embodiment, the interconnect substrate may be formed by forming a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern using a solution (ie, a lift-off method).

[0231] The present disclosure will be described in more detail using the following examples and comparative examples, but the technical scope of the present disclosure is not limited only to the following non-limiting examples.

[0232] [Example]

[0233] Synthesis Example 1: Synthesis of SM1

[0234]

[0235] 8.2 g (69.2 mmol) of Sn powder and 120 ml of dry toluene were added to a 250 ml three-necked flask, and the temperature was raised to 90° C. About 1.0 ml of DI water was added thereto, and then 10.0 g (69.2 mmol) of 4-fluorobenzyl chloride was added dropwise for 10 minutes. Heating, reflux, and stirring were performed at 130° C. for 4 hours, and then unreacted Sn powder was filtered out using a Buchner funnel. Meanwhile, as the filtered solution cooled, 6.5 g of white crystals (SM1 precursor) were obtained as a product (36% yield).

[0236]

[0237] 1.5 g (3.7 mmol) of SM1 precursor and 21.0 ml of dry acetone were added to a 50 ml single-necked flask, and the temperature was lowered to 0° C. 0.6 g (7.4 mmol) of sodium acetate was added thereto, and then, stirred for about 12 hours. The NaCl salt produced in the solution was filtered using a 0.45 μm filter, and the resulting solution was concentrated by rotary evaporation and dried under vacuum to obtain SM1 (1.6 g) in a yield of 74%.

[0238] 1 H-NMR (500 MHz, DMSO-d 6 ): δ~6.9(8H),~2.6(4H),~1.6(6H)

[0239] Preparation Example: Preparation of Casting Solution

[0240] The organometallic compound synthesized in Synthesis Example 1 was dissolved in ethyl lactate at 2 wt %, and then 0.5 equivalent (based on the amount of the organometallic compound as 1 equivalent) of the additives shown in Table 1 below was added and mixed to prepare casting solutions A-1 to A-4.

[0241] The casting solution A-1 to the casting solution A-4 were stored in an oven at 40° C. for 12 days to obtain casting solutions B-1 to B-4.

[0242] [Table 1]

[0243]

[0244]

[0245] The post-treatment in Table 1 refers to storage in an oven at 40°C for 12 days.

[0246] Evaluation Example 1: Storage stability evaluation

[0247] (1) Visual evaluation

[0248] For casting solutions B-1 to B-4, the change over time was determined with naked eyes. Casting solutions B-2 to B-4 containing additives showed no change over time, while casting solution B-1 without additives showed visible change.

[0249] (2) Surface roughness (Rq) evaluation

[0250] An 8-inch diameter silicon wafer was cut into four equal parts and 2 The films were plasma treated for 30 minutes, and each of the casting solutions A-1 to A-4 and the casting solutions B-1 to B-4 was spin-coated at 1500 rpm for 1 minute, followed by pre-baking (PB) at 120° C. for 1 minute, thereby producing films having the initial thicknesses shown in Table 2. Then, a 3.5 mm thick mask (4 cm×4 cm) having rectangular holes (1 cm×1 cm) was placed on the films obtained using the casting solutions B-1 to B-4, and each hole was irradiated with 0 mJ / cm 2 Up to 100mJ / cm 2 The film was exposed to a deep ultraviolet (DUV) line at a wavelength of 254 nm with a dose of 1000 nm, and the resulting structure was post-exposure baked (PEB) at 200° C. for 1 minute. The post-exposure baked film was immersed at 25° C. for 60 seconds using a PGMEA solution containing 2 wt % acetic acid as a developer, and then the surface of the remaining film was identified by atomic force microscopy, and Rq was calculated from the average value of the observed height, and the results are listed in Table 2 below.

[0251] [Table 2]

[0252] Casting solution number Initial thickness (nm) Rq(nm) Comparative Example 1-1 A-1 23.69 - Example 1-1 A-2 25 - Example 1-2 A-3 22 - Examples 1-3 A-4 20.52 - Comparative Example 2-1 B-1 8.23 0.385 Example 2-1 B-2 23.53 0.314 Example 2-2 B-3 20.29 0.297 Example 2-3 B-4 22.64 0.317

[0253] Referring to Table 2, in the case of Comparative Example 2-1 without additives, the thickness of the film formed after storage at high temperature was significantly reduced compared with that before storage, confirming that the storage stability was low, while in the cases of Examples 2-1 to 2-3 to which additives were added, even after high-temperature storage, the film thickness was able to be maintained at a level similar to that before storage, confirming that the storage stability was relatively high.

[0254] In addition, in the case of Examples 2-1 to 2-3 in which the additive was added, Rq was smaller than that of Comparative Example 2- 1. As a result, it was confirmed that the coating characteristics of the resist composition to which the additive was added were improved.

[0255] Evaluation Example 2: Evaluation of Thin Film Development

[0256] 2 wt % of SM1 obtained in Synthesis Example 1 was dissolved in ethyl lactate, and 0.2 equivalent of 1,10-phenanthroline was further added thereto as an additive (SM1:1,10-phenanthroline=12:1 (mass ratio)) to obtain a casting solution C-1. At the same time, a casting solution C-2 having the same composition as the casting solution C-1 was obtained, except that 1,10-phenanthroline was not added. A silicon wafer having a diameter of 4 inches was washed with O 2 The films were plasma treated for 30 minutes, spin-coated with casting solution C-1 and casting solution C-2 at 1200 rpm for 1 minute each, and then pre-baked (PB) at 90° C. for 1 minute to produce films with the initial thicknesses shown in Table 3 below. Then, a 3.5 mm thick mask (4 cm×4 cm) with rectangular holes (1 cm×1 cm) was placed thereon, and each hole was irradiated with 0 mJ / cm 2 Up to 100mJ / cm 2 The film was exposed to DUV light of a wavelength of 254 nm at a dose of 1000 nm, and the resulting structure was post-exposure baked (PEB) at 200° C. for 1 minute. The post-exposure baked film was immersed in a PGMEA solution containing 2 wt % acetic acid as a developer for 60 seconds. The thickness of the remaining film was measured and is shown in Table 3 and Figure 3A and 3B About Figure 3A and 3B , the term “as applied” refers to the reference data of the sample after PB, the term “after PEB” refers to the reference data of the sample after PEB but before treatment with the developer, and the term “after development” refers to the reference data of the sample that has been treated with the developer.

[0257] [Table 3]

[0258]

[0259] In Table 3, E th refers to the exposure at the point when the film begins to harden, and E 1 Refers to the exposure at the saturation point where the thickness of the film no longer increases.

[0260] Referring to Table 3, it can be seen that the E th and E 1 E is in the same range as that of Comparative Example 3-1 th and E 1 From this result, it can be confirmed that the photosensitivity does not decrease even when the additive is used.

[0261] Figures 4A to 4E is a side-sectional view illustrating a method of forming a patterned structure according to an embodiment.

[0262] Reference Figure 4A , before forming the resist film 110 on the substrate 100, a material layer 130 may be 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 be a multilayer structure. The material of the material layer 130 may be different from the material of the substrate 100. The resist film 110 may include a resist composition according to an example embodiment, and may have a thickness of about 10 nm to about 300 nm, or about 30 nm to about 200 nm.

[0263] Reference Figure 4B , the resist film 110 may be exposed to high energy rays through the mask 120 , after which the resist film 110 may include an exposed portion 111 and an unexposed portion 112 .

[0264] Reference Figure 4C In order to form the resist pattern 110, a developer (eg, a developing solution) may be used to develop the exposed resist film 110. The exposed portion 111 may remain without being washed away by the developer, while the unexposed portion 112 may be washed away by the developer.

[0265] Reference Figure 4D , the exposed region of the material layer 130 may be etched using the resist pattern 110 as a mask to form a material pattern 135 on the substrate 100 .

[0266] Reference Figure 4E , the resist pattern 110 may be removed.

[0267] Figures 5A to 5E is a side cross-sectional view illustrating a method of forming a semiconductor device according to an embodiment.

[0268] Reference Figure 5A , a gate dielectric 505 (eg, 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 (eg, doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0269] Reference Figure 5B , a resist pattern 540b may be formed on the hard mask layer 520. The resist pattern 540b may be formed using a resist composition according to example embodiments. The resist pattern 540b may be formed of a resist composition according to example embodiments.

[0270] Reference Figure 5C, the hard mask layer 520, the gate layer 515, and the gate dielectric 505 may be etched by using the resist pattern 540b as a mask to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a. Then, the resist pattern 540b and the hard mask pattern 520a may be removed.

[0271] Reference Figure 5D , the hard mask pattern 520a may be optionally removed and a spacer layer may be formed on the gate electrode pattern 515a and the gate dielectric pattern 505a. The spacer layer may be formed using a deposition process (e.g., CVD). The spacer layer 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 forming the spacers 535a, ions may be implanted into the substrate 500 to form source / drain impurity regions S / D.

[0272] Reference Figure 5E , an interlayer insulating layer 560 (e.g., oxide) may be formed on the substrate 500 to cover the gate electrode pattern 515a, the gate dielectric pattern 505a, and the spacer 535a. Then, electrical contacts 570a, 570b, and 570c may be formed in the interlayer insulating layer 560 to connect to the gate electrode 515a and the S / D region. The electrical contacts 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 layer 560 and the electrical contacts 570a, 570b, and 570c. Although Figures 5A to 5E An example of forming a transistor is shown, but the inventive concept is not limited thereto.

[0273] The resist composition according to one or more embodiments may be used in a patterning process to form other types of semiconductor devices.

[0274] According to an embodiment, a resist composition having improved storage stability and improved sensitivity and providing a pattern with increased resolution may be provided.

[0275] It should be understood that the embodiments described herein should be considered in a descriptive sense only and not for limiting purposes. The description of features or aspects in each embodiment should typically be considered to be applicable to other similar features or aspects in other embodiments. Although one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope as defined by the appended claims.

Claims

1. A resist composition comprising: An organometallic compound represented by one of Formulae 1-1 to 1-4; and The additive represented by Formula 2, Formula 2 Wherein, in Formulas 1-1 to 1-4 and 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), L 11 To L 14 Each is independently a single bond or a substituted or unsubstituted linear, branched or cyclic C1-C 30 Divalent hydrocarbon groups, a11 to a14 are each independently an integer of 1 to 4, and R 11 To R 14 are each independently substituted or unsubstituted C3-C 30 Branched alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Heterocycloalkyl, substituted or unsubstituted C2-C 30 Alkenyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C3-C 30 Heterocycloalkenyl, substituted or unsubstituted C2-C 30 Alkynyl, 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 Adjacent two of are optionally bonded to each other to form a ring, b11 to b14 are each independently an integer from 1 to 4, Y 11 To Y 13 Each independently represents O, OC(=O), S, SC(=O), NX 14 , or NX 14 C(=O), X 11 To X 14 are each independently hydrogen, deuterium, or a substituted or unsubstituted linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, Y 21 and Y 22 are each independently a substituted or unsubstituted linear, branched or cyclic C1-C1-C2- 30 Monovalent hydrocarbon groups, L 21 is a single bond, a double bond, or a substituted or unsubstituted straight-chain, branched or cyclic C1-C 30 Divalent hydrocarbon groups, a21 is an integer from 1 to 4, and Y 21 , Y 22 , and L 21 Adjacent two of are optionally bonded to each other to form a fused ring.

2. The resist composition according to claim 1, wherein M 11 is In, Sn, or Sb.

3. The resist composition according to claim 1, wherein L 11 To L 14 are each independently a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocycloalkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Heterocycloalkenylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C1-C 30 Heteroarylene.

4. The resist composition according to claim 1, wherein R 11 To R 14 Each independently selected from a branched C3-C 30 Alkyl, C3-C 30 Cycloalkyl, C3-C 30 Heterocycloalkyl, C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 30 Aryl, C7-C 30 Arylalkyl, C1-C 30 Heteroaryl, and C2-C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof.

5. The resist composition according to claim 1, wherein The organometallic compound is represented by one of Formulas 1-1 to 1-3, Y 11 To Y 13 Each is independently O, OC(═O), S, or SC(═O).

6. The resist composition according to claim 1, wherein X 11 To X 14 are each independently selected from: hydrogen; deuterium; and C1-C 30 Alkyl, C1-C 30 Halogenated alkyl, C1-C 30 Alkoxy, C1-C 30 Alkylthio, C1-C 30 Halogenated alkoxy, C1-C 30 Halogenated alkylthio, C3-C 30 Cycloalkyl, C3-C 30 Cycloalkoxy, C3-C 30 Cycloalkylthio, C3-C 30 Heterocycloalkyl, C2-C 30 Alkenyl, C3-C 30 Cycloalkenyl, C3-C 30 Heterocycloalkenyl, C2-C 30 Alkynyl, C6-C 30 Aryl, C6-C 30 Aryloxy, C6-C 30 Arylthio, C7-C 30 Arylalkyl, C1-C 30 Heteroaryl, C1-C 30 Heteroaryloxy, C1-C 30 Heteroarylthio, and C2-C 30 Heteroarylalkyl: deuterium, halogen atom, cyano group, nitro group, hydroxyl group, thiol group, amino group, carboxylate group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 Alkyl, C1-C 20 Halogenated alkyl, C1-C 20 Alkoxy, C1-C 20 Alkylthio, C1-C 20 Halogenated alkoxy, C1-C 20 Halogenated alkylthio, C3-C 20 Cycloalkyl, C3-C 20 Cycloalkoxy, C3-C 20 Cycloalkylthio, C6-C 20 Aryl, C1-C 20 Heteroaryl, C6-C 20 Aryloxy, C6-C 20 Arylthio, C1-C 20 Heteroaryloxy, C1-C 20 heteroarylthio, or a combination thereof.

7. The resist composition according to claim 1, wherein The organometallic compound represented by one of Formulae 1-1 to 1-4 is selected from Group I: Group I Wherein n in group I is an integer from 1 to 4.

8. The resist composition according to claim 1, wherein Y 21 It is represented by one of Formulas 4-1 to 4-5, and Y 22 It is represented by one of the formulas 4-6 to 4-10: in, In formulas 4-1 to 4-10, X 41 and X 44 Each independently is N or P, X 42 and X 45 are each independently O or S, X 43 and X 46 are each independently O, S, N, or P, Y in formula 4-3 and 4-8 41 and Y 42 Each independently is C or S, Y in formula 4-4 and 4-9 41 and Y 42 Each is P, A 41 To include X 43 C1-C as a ring member 30 Heterocyclic groups, A 42 To include X 46 C1-C as a ring member 30 Heterocyclic groups, R 41 To R 44 are each independently hydrogen, deuterium, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylate group, or a substituted or unsubstituted linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, b41 and b42 are each independently an integer from 1 to 10, and *Indicates the binding site with the adjacent atom.

9. The resist composition according to claim 8, wherein A 41 and A 42 are each independently 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 to each other, or iii) a monovalent group derived from a fused ring in which one or more first rings are fused to one or more second rings, 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.

10. The resist composition according to claim 8, wherein Y 21 It is represented by formula 4-5, and Y 22 is represented by one of Formulas 4-6 to 4-10, or Y 21 is represented by one of Formulas 4-1 to 4-5, and Y 22 Expressed by formula 4-10.

11. The resist composition according to claim 1, wherein L 21 is a single bond, double bond, substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C3-C 30 Cycloalkylene, substituted or unsubstituted C3-C 30 Heterocycloalkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Heterocycloalkenylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C1-C 30 Heteroarylene.

12. The resist composition according to claim 1, wherein The additive is represented by formula 2-1: in, In formula 2-1, X 43 and X 46 are each independently O, S, N, or P, A 41 To include X 43 C1-C as a ring member 30 Heterocyclic groups, A 42 To include X 46 C1-C as a ring member 30 Heterocyclic groups, L 21 is a single bond, a double bond, or a substituted or unsubstituted straight-chain, branched or cyclic C1-C 30 Divalent hydrocarbon groups, a21 is an integer from 1 to 4, R 41 and R 43 are each independently a substituted or unsubstituted linear, branched or cyclic C1-C 30 Monovalent hydrocarbon groups, b41 and b42 are each independently an integer from 1 to 10, and R 41 , R 43 , and L 21 Adjacent two of are optionally bonded to each other to form a fused ring.

13. The resist composition according to claim 1, wherein The additive is selected from Group II: Group II 14. The resist composition according to claim 1, wherein The additive is included in an amount of 0.1 parts by weight to 100,000 parts by weight based on 100 parts by weight of the organic metal compound.

15. The resist composition according to claim 1, wherein The resist composition does not include a photoacid generator.

16. The resist composition according to claim 1, wherein The resist composition substantially does not include a compound having a molecular weight of 1,000 g / mol or more other than the organic metal compound.

17. A pattern forming method comprising: Forming a resist film by applying the resist composition according to any one of claims 1 to 16 on a substrate; exposing at least a portion of the resist film to high energy radiation to provide an exposed resist film; as well as The exposed resist film is developed using a developer.

18. The pattern forming method according to claim 17, wherein Exposing at least a portion of the resist film is performed by irradiating at least one of deep ultraviolet (DUV) rays, extreme ultraviolet (EUV) rays, or electron beams (EB).

19. The pattern forming method according to claim 17, wherein The organometallic compound undergoes a cross-linking reaction during exposure of at least a portion of the resist film.

20. The pattern forming method according to claim 17, wherein The exposed resist film includes an exposed portion and an unexposed portion, and In the development, the unexposed portion is removed.

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