Resist composition and method of forming pattern using the same

Abstract

To provide a resist composition and a method of forming a pattern using the same.SOLUTION: Provided are a resist composition including an organometallic compound represented by the following formula 1 and an additive represented by the following formula 2, and a pattern formation method using the same. In formulae 1 and 2, M11, Rx, Ry, n, m, A21, L21 to L23, a21-a23, R21, R22, b21, b22, X21, o, p and q are as described in the specification.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a resist composition and a pattern forming method using the same.

Background Art

[0002] When manufacturing semiconductors, a resist that changes its physical properties in response to light is used to form fine patterns. Among them, chemically amplified resists have been widely used. In a chemically amplified resist, an acid formed by the reaction of light and a photoacid generator reacts again with a base resin, changing the solubility of the base resin in a developer, thereby enabling patterning.

[0003] However, in the case of a chemically amplified resist, as the formed acid diffuses to the unexposed area, problems such as a decrease in pattern uniformity and an increase in surface roughness are caused. Also, as semiconductor processes become increasingly miniaturized, it is not easy to control the diffusion of the acid, and new types of resist development are required.

[0004] In recent years, in order to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change upon exposure. However, there is still a problem that the dose required during exposure is high.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide a resist composition having improved storage stability, whose physical properties change even with low-dose exposure, and which provides a pattern with improved resolution, and a pattern forming method using the same.

Means for Solving the Problems

[0006] Provided is a resist composition containing, on one side, an organometallic compound represented by the following Chemical Formula 1 and an additive represented by the following Chemical Formula 2: [Chemical Formula] In the above Chemical Formulas 1 and 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), R x is *-(L1) a1 -(R1) b1 where R y is *-Y1-X1, n is an integer from 1 to 6, m is an integer from 0 to 6, m - n is 0 or more, A plurality of R x may be the same as or different from each other, A plurality of R y may be the same as or different from each other, L1 is a single bond or a linear, branched, or cyclic divalent hydrocarbon group of C1-C 30 optionally containing a heteroatom, a1 is an integer from 1 to 4, R1 is a substituted or unsubstituted C1-C 30 alkyl group, a substituted or unsubstituted C3-C 30 cycloalkyl group, a substituted or unsubstituted C3-C 30 heterocycloalkyl group, a substituted or unsubstituted C2-C 30 alkenyl group, a substituted or unsubstituted C3-C 30 cycloalkenyl group, a substituted or unsubstituted C3-C 30 heterocycloalkenyl group, a substituted or unsubstituted C2-C 30 alkynyl group, a substituted or unsubstituted C6-C 30 aryl group, a substituted or unsubstituted C7-C 30An arylalkyl group, a substituted or unsubstituted C1-C 30 heteroaryl group, or a substituted or unsubstituted C2-C 30 heteroarylalkyl group, and among a plurality of R1, two adjacent groups can optionally be bonded to each other to form a fused ring, b1 is an integer from 1 to 4, Y1 is O, O(C=O), S, S(C=O), NX 14 , or NX 14 (C=O), X1 and X 14 are each independently hydrogen, deuterium, or a C1-C 30 linear, branched, or cyclic monovalent hydrocarbon group that may optionally contain a heteroatom, A 21 is a single bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, or a (p+q)-valent bonding unit, L 21 ~L 23 are each independently a single bond; O; S; CO; CO2; a C1-C 30 linear, branched, or cyclic divalent hydrocarbon group that may optionally contain a heteroatom; or any combination thereof, a21~a23 are each independently an integer from 1 to 6, R 21 and R 22 are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, or a C1-C 30 linear, branched, or cyclic monovalent hydrocarbon group that may optionally contain a heteroatom, b21 is an integer from 1 to 4, b22 is an integer from 1 to 5, X 21 is a substituted or unsubstituted C1-C 30 alkyl group, a substituted or unsubstituted C1-C 30 haloalkyl group, a substituted or unsubstituted C2-C 30 alkenyl group, or a substituted or unsubstituted C6-C 30is an aryl group, o is an integer from 1 to 10, p is an integer from 1 to 10, q is an integer from 0 to 10, A 21 , L 21 ~L 23 , R 21 and R 22 Any two adjacent ones of them can optionally be bonded to each other to form a ring.

[0007] According to another aspect, there is provided a patterning method including applying the aforementioned resist composition onto a substrate to form a resist film, exposing at least a part of the resist film with high energy rays, and developing the exposed resist film using a developer.

Advantages of the Invention

[0008] Embodiments of the present invention can provide a resist composition having improved storage stability and improved sensitivity, and providing a pattern with improved resolution.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2A

Figure 2B

Figure 2C

Modes for Carrying Out the Invention

[0010] The present invention can be subjected to various transformations and can have various embodiments. Specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and the present invention should be understood to include all transformations, equivalents, or alternatives included in the spirit and technical scope of the present invention. When a specific description of related known technologies in explaining the present invention is determined to obscure the gist of the present invention, the detailed description thereof will be omitted.

[0011] Terms such as "first," "second," "third," etc. are used to describe various components, but are used only for the purpose of distinguishing one component from another, and the order, type, etc. of the components are not limited.

[0012] As used herein, descriptions that a portion such as a layer, film, region, plate, etc. is "above" or "on" another portion include not only those immediately above, below, left, or right in contact, but also those above, below, left, or right without contact.

[0013] Singular expressions include plural expressions unless clearly stated otherwise in the context. Terms such as "comprising" or "having" represent the presence of the features, numbers, steps, operations, components, parts, elements, materials, or combinations thereof described in the specification, unless otherwise stated to the contrary, and do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, elements, materials, or combinations thereof.

[0014] Whenever a range of values is recited, that range includes all values falling within the range as explicitly recited, including the boundaries of the range. Thus, a range of "X to Y" includes all values between X and Y, including X and Y.

[0015] As used herein, "C x -C y" means that the number of carbons constituting the substituent is from x to y. For example, "C1-C6" means that the number of carbons constituting the substituent is from 1 to 6, and "C6-C 20 " means that the number of carbons constituting the substituent is from 6 to 20.

[0016] As used herein, the term "monovalent hydrocarbon group" means a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples include linear or branched alkyl groups (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, 2-ethylhexyl group, and nonyl group); monovalent saturated cycloaliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, 1-adamantyl group, 2-adamantyl group, 1-adamantylmethyl group, norbornyl group, norbornylmethyl group, tricyclodecanyl group, tetracyclododecanyl group, tetracyclododecanylmethyl group, and dicyclohexylmethyl group); monovalent unsaturated aliphatic hydrocarbon groups (alkenyl groups, alkynyl groups) (e.g., allyl group); monovalent unsaturated cycloaliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl); aryl groups (e.g., phenyl group, 1-naphthyl group, and 2-naphthyl group); arylalkyl groups (e.g., benzyl group and diphenylmethyl group); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, methylthiomethyl group, acetamidomethyl group, trifluoroethyl group, (2-methoxyethoxy)methyl group, acetoxymethyl group, 2-carboxy-1-cyclohexyl group, 2-oxopropyl group, 4-oxo-1-adamantyl group, and 3-oxocyclohexyl group), or any combination thereof, etc. may be included.Also, in these groups, some of the hydrogens are replaced by moieties containing heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, or halogen atoms, or some of the carbons are replaced by moieties containing heteroatoms such as oxygen, sulfur, nitrogen, or phosphorus. Therefore, these groups include cyano groups, nitro groups, hydroxy groups, thiol groups, amino groups, carboxylic acid groups, ether moieties, thioether moieties, carbonyl moieties, ester moieties, phosphonate moieties, sulfonate moieties, carbonate moieties, amide moieties, lactone moieties, sultone moieties, carboxylic acid anhydride moieties, and the like.

[0017] As used herein, the "divalent hydrocarbon group" is a divalent residue, which means that one hydrogen of any one of the monovalent hydrocarbon groups is replaced by a bonding site with an adjacent atom. The divalent hydrocarbon group may include, for example, linear or branched alkylene groups, cycloalkylene groups, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, and those in which some of their carbons are replaced by heteroatoms.

[0018] As used herein, the "alkyl group" means a linear or branched saturated aliphatic hydrocarbon monovalent group. Specific examples include methyl group, ethyl group, propyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, and the like. As used herein, the "alkylene group" means a linear or branched saturated aliphatic hydrocarbon divalent group. Specific examples include methylene group, ethylene group, propylene group, butylene group, isobutylene group, and the like.

[0019] As used herein, the "halogenated alkyl group" means a group in which one or more substituents of the alkyl group are replaced by halogens. Specific examples include CF3 and the like. Here, the halogen is F, Cl, Br, or I.

[0020] As used herein, the "alkoxy group" means a monovalent group having the chemical formula of -OA 101 where A101 is an alkyl group. Specific examples thereof include a methoxy group, an ethoxy group, an isopropyloxy group, and the like.

[0021] In this specification, the "alkylthio group" means a monovalent group having the chemical formula -SA 101 wherein A 101 is an alkyl group.

[0022] In this specification, the "halogenated alkoxy group" means a group in which one or more hydrogens of the alkoxy group are substituted with a halogen, and specific examples thereof include -OCF3 and the like.

[0023] In this specification, the "halogenated alkylthio group" means a group in which one or more hydrogens of the alkylthio group are substituted with a halogen, and specific examples thereof include -SCF3 and the like.

[0024] In this specification, the "cycloalkyl group" means a monovalent saturated hydrocarbon cyclic group, and specific examples thereof include monocyclic groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and condensed polycyclic groups such as a norbornyl group and an adamantyl group. In this specification, the "cycloalkylene group" means a divalent saturated hydrocarbon cyclic group, and specific examples thereof include a cyclopentylene group, a cyclohexylene group, an adamantylene group, an adamantylmethylene group, a norbornylene group, a norbornylmethylene group, a tricyclodecanylene group, a tetracyclododecanylene group, a tetracyclododecanylmethylene group, a dicyclohexylmethylene group, and the like.

[0025] In this specification, the "cycloalkoxy group" means a monovalent group having the chemical formula -OA 102 wherein A 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like.

[0026] In this specification, the "cycloalkylthio group" means a monovalent group having the chemical formula -SA 102 wherein A 102is a cycloalkyl group.

[0027] As used herein, the "heterocycloalkyl group" is a moiety in which some of the carbon atoms of the cycloalkyl group are replaced by heteroatoms such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group specifically includes an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic acid anhydride moiety. As used herein, the "heterocycloalkylene group" is a moiety in which some of the carbon atoms of the cycloalkylene group are replaced by heteroatoms such as oxygen, sulfur, or nitrogen.

[0028] As used herein, the "heterocycloalkoxy group" means a monovalent group having the chemical formula -OA 103 , where A 103 is a heterocycloalkyl group.

[0029] As used herein, the "heterocycloalkylthio group" means a monovalent group having the chemical formula -SA 103 , where A 103 is a heterocycloalkyl group.

[0030] As used herein, the "alkenyl group" means a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, the "alkenylene group" means a straight-chain or branched unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds.

[0031] As used herein, the "cycloalkenyl group" means a monovalent unsaturated hydrocarbon cyclic group containing one or more carbon-carbon double bonds. As used herein, the "cycloalkenylene group" means a divalent unsaturated hydrocarbon cyclic group containing one or more carbon-carbon double bonds.

[0032] As used herein, the "heterocycloalkenyl group" is a moiety in which some of the carbon atoms of the cycloalkenylene group are replaced by a heteroatom-containing moiety, such as oxygen, sulfur, or nitrogen. As used herein, the "heterocycloalkenylene group" is a moiety in which some of the carbon atoms of the cycloalkenylene group are replaced by a heteroatom-containing moiety, such as oxygen, sulfur, or nitrogen.

[0033] As used herein, the "alkynyl group" means a straight-chain or branched unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds.

[0034] As used herein, the "aryl group" means a monovalent group having an aromatic carbocyclic system, and specific examples include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, and the like. As used herein, the "arylene group" means a divalent group having an aromatic carbocyclic system.

[0035] As used herein, the "aryloxy group" means a monovalent group having the chemical formula -OA 104 wherein A 104 is an aryl group.

[0036] As used herein, the "arylthio group" means a monovalent group having the chemical formula -SA 104 wherein A 104 is an aryl group.

[0037] As used herein, the "heteroaryl group" means a monovalent group having a heterocyclic aromatic system, and specific examples include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, and the like. As used herein, the "heteroarylene group" means a divalent group having a heterocyclic aromatic system.

[0038] As used herein, the "heteroaryloxy group" means a monovalent group having the chemical formula -OA 105 wherein A 105 is a heteroaryl group.

[0039] In this specification, the "heteroarylthio group" means a monovalent group having the chemical formula of -SA 105 , where A 105 is a heteroaryl group.

[0040] In this specification, the "arylalkyl group" means a group in which a monovalent group having a carbocyclic aromatic system is substituted on an alkyl group, and specific examples include a benzyl group, a diphenylmethyl group, and the like.

[0041] In this specification, the "heteroarylalkyl group" means a group in which a monovalent group having a heterocyclic aromatic system is substituted on an alkyl group.

[0042] In this specification, the "heterocyclic group" means a monocyclic group or a polycyclic group having 1 to 60 carbon atoms and containing at least one heteroatom, and is a group including any of monovalent, divalent, trivalent, etc.

[0043] In this specification, the "substituent" is deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryl group, C1-C20 A heteroaryloxy group, or a C1-C 20 heteroarylthio group; Deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid 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 group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryl group, C1-C 20 heteroaryloxy group, C1-C 20 heteroarylthio group, and a C1-C substituted by any combination thereof 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryl group, C1-C20 A heteroaryloxy group, and C1-C 20 A heteroarylthio group; and any combination thereof.

[0044] Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings. When describing with reference to the drawings, substantially the same or corresponding components are given the same drawing numbers, and redundant descriptions thereof are omitted. In the drawings, the thickness is enlarged to clearly show a plurality of layers and regions. And, in the drawings, for convenience of explanation, the thicknesses of some layers and regions are exaggerated. On the other hand, the embodiments described below are merely exemplary, and various modifications are possible from such embodiments.

[0045] [Resist composition] A resist composition according to an exemplary embodiment includes an organometallic compound represented by the following Chemical Formula 1 and an additive represented by the following Chemical Formula 2: [Chemical formula] In the above Chemical Formulas 1 and 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), R x is *-(L1) a1 -(R1) b1 wherein R y is *-Y1-X1, n is an integer from 1 to 6, m is an integer from 0 to 6, m - n is 0 or more, A plurality of R x may be the same as or different from each other, A plurality of R y may be the same as or different from each other, L1 is a single bond, or a linear, branched or cyclic divalent hydrocarbon group of C1-C 30 and is a linear, branched or cyclic divalent hydrocarbon group, a1 is an integer from 1 to 4, R1 is a substituted or unsubstituted C1-C 30 alkyl group, a substituted or unsubstituted C3-C 30 cycloalkyl group, a substituted or unsubstituted C3-C 30 heterocycloalkyl group, a substituted or unsubstituted C2-C 30 alkenyl group, a substituted or unsubstituted C3-C 30 cycloalkenyl group, a substituted or unsubstituted C3-C 30 heterocycloalkenyl group, a substituted or unsubstituted C2-C 30 alkynyl group, a substituted or unsubstituted C6-C 30 aryl group, a substituted or unsubstituted C7-C 30 arylalkyl group, a substituted or unsubstituted C1-C 30 heteroaryl group, or a substituted or unsubstituted C2-C 30 heteroarylalkyl group, and among a plurality of R1, two adjacent groups can optionally be bonded to each other to form a fused ring, b1 is an integer from 1 to 4, Y1 is O, O(C=O), S, S(C=O), NX 14 , or N(C=O), X1 and X 14 are each independently hydrogen, deuterium, or a C1-C 30 linear, branched or cyclic monovalent hydrocarbon group which may optionally contain a heteroatom, A 21 is a single bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, or a (p+q)-valent bonding unit, L 21 ~L 23 are each independently a single bond; O; S; CO; CO2; a C1-C 30 linear, branched or cyclic divalent hydrocarbon group which may optionally contain a heteroatom; or any combination thereof, a21 to a23 are each independently an integer from 1 to 6, R 21 and R22 is, independently of each other, hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, or a C1-C optionally containing a heteroatom 30 which is a linear, branched or cyclic monovalent hydrocarbon group, b21 is an integer from 1 to 4, b22 is an integer from 1 to 5, X 21 is a substituted or unsubstituted C1-C 30 alkyl group, a substituted or unsubstituted C1-C 30 haloalkyl group, a substituted or unsubstituted C2-C 30 alkenyl group, or a substituted or unsubstituted C6-C 30 aryl group, o is an integer from 1 to 10, p is an integer from 1 to 10, q is an integer from 0 to 10, A 21 、L 21 ~L 23 、R 21 and R 22 Among them, two adjacent ones can optionally be bonded to each other to form a ring.

[0046] The molecular weight of the organometallic compound is 3000 g / mol or less. Specifically, the molecular weight of the organometallic compound is 2000 g / mol or less.

[0047] Without being limited to a specific theory, radicals are formed from the organometallic compound by heat and / or high-energy rays. Specifically, radicals are formed from the M 11 -carbon bond, and optionally in an atmosphere where water is present in some cases, the radicals react to form a chemical bond between the organometallic compounds. Thereby, the physical properties of the organometallic compound, particularly the solubility in the developer, can change.

[0048] In addition, since the organometallic compound has a ligand with a specific structure, it can have improved photosensitivity, stability, and / or coating properties.

[0049] For example, in Chemical Formula 1, M 11 is In, Sn, or Sb. Specifically, in Chemical Formula 1, M 11 is Sn.

[0050] In Chemical Formula 1, m represents the valence of M 11 .

[0051] For example, in Chemical Formula 1, n is an integer from 1 to 4.

[0052] For example, in Chemical Formula 1, m is an integer from 0 to 3.

[0053] In one embodiment, in Chemical Formula 1, n is an integer from 1 to 4, m is an integer from 0 to 3, and M 11 is Sn.

[0054] For example, in Chemical Formula 1, L1 is a single bond, a substituted or unsubstituted C1-C 30 alkylene group, a substituted or unsubstituted C3-C 30 cycloalkylene group, a substituted or unsubstituted C3-C 30 heterocycloalkylene group, a substituted or unsubstituted C2-C 30 alkenylene group, a substituted or unsubstituted C3-C 30 cycloalkenylene group, a substituted or unsubstituted C3-C 30 heterocycloalkenylene group, a substituted or unsubstituted C6-C 30 arylene group, or a substituted or unsubstituted C1-C 30 heteroarylene group.

[0055] Specifically, in the chemical formula 1, L1 is a single bond; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C1-C 20 heteroaryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryloxy group, C1-C 20 heteroarylthio group, or a C1-C substituted or unsubstituted with any combination thereof 30 alkylene group, C3-C 30 cycloalkylene group, C3-C 30 heterocycloalkylene group, C2-C 30 alkenylene group, C3-C 30 cycloalkenylene group, C3-C 30 heterocycloalkenylene group, C6-C 30 arylene group, and C1-C 30 heteroarylene group; selected from. More specifically, in the chemical formula 1, L1 is a single bond; and deuterium, halogen, hydroxy group, cyano group, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, or a C1-C substituted or unsubstituted with any combination thereof 30Selected from an alkylene group;

[0056] For example, in Chemical Formula 1 above, a1 is an integer of 1 or 2.

[0057] For example, in Chemical Formula 1 above, R1 is deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C1-C 20 heteroaryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryloxy group, C1-C 20 heteroarylthio group, or a C1-C substituted or unsubstituted with any combination thereof 30 alkyl group, C3-C 30 cycloalkyl group, C3-C 30 heterocycloalkyl group, C2-C 30 alkenyl group, C3-C 30 cycloalkenyl group, C3-C 30 heterocycloalkenyl group, C2-C 30 alkynyl group, C6-C 30 aryl group, C7-C 30 arylalkyl group, C1-C 30 heteroaryl group, and C2-C30 It is selected from a heteroarylalkyl group.

[0058] Specifically, in the chemical formula 1, R1 is deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20 cycloalkylthio group, C6-C 20 aryl group, C1-C 20 heteroaryl group, C6-C 20 aryloxy group, C6-C 20 arylthio group, C1-C 20 heteroaryloxy group, C1-C 20 heteroarylthio group, or a C1-C substituted or unsubstituted with any combination thereof 30 alkyl group, C3-C 30 cycloalkyl group, C2-C 30 alkenyl group, C3-C 30 cycloalkenyl group, C2-C 30 alkynyl group, C6-C 30 aryl group, and C7-C 30 It is selected from an arylalkyl group.

[0059] More specifically, in the chemical formula 1, R1 is selected from any one of the following chemical formulas 3-1 to 3-15:

Chemical formula

[0060] In the above chemical formulas 3-1 to 3-15, at least one hydrogen is optionally substituted with deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, or any combination thereof, and may be optionally substituted.

[0061] In the above chemical formula 1, b1 represents the number of substituents of R1. For example, in the above chemical formula 1, b1 is 1 or 2.

[0062] For example, in the above chemical formula 1, Y1 is O, O(C=O), S, or S(C=O).

[0063] For example, in the above chemical formula 1, X1 and X 14 are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid 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 group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 alkylthio group, C1-C 20 halogenated alkoxy group, C1-C 20 halogenated alkylthio group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C3-C 20A cycloalkylthio group, C6-C 20 An aryl group, C1-C 20 A heteroaryl group, C6-C 20 An aryloxy group, C6-C 20 An arylthio group, C1-C 20 A heteroaryloxy group, C1-C 20 A heteroarylthio group, or a C1-C optionally substituted or unsubstituted by any combination thereof 30 An alkyl group, C1-C 30 A halogenated alkyl group, C1-C 30 An alkoxy group, C1-C 30 An alkylthio group, C1-C 30 A halogenated alkoxy group, C1-C 30 A halogenated alkylthio group, C3-C 30 A cycloalkyl group, C3-C 30 A cycloalkoxy group, C3-C 30 A cycloalkylthio group, C3-C 30 A heterocycloalkyl group, C2-C 30 An alkenyl group, C3-C 30 A cycloalkenyl group, C3-C 30 A heterocycloalkenyl group, C2-C 30 An alkynyl group, C6-C 30 An aryl group, C6-C 30 An aryloxy group, C6-C 30 An arylthio group, C7-C 30 An arylalkyl group, C1-C 30 A heteroaryl group, C1-C 30 A heteroaryloxy group, C1-C 30 A heteroarylthio group, and C2-C 30 A heteroarylalkyl group; selected from.

[0064] Specifically, in the chemical formula 1, X1 and X 14are each independently hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C3-C 20 cycloalkyl group, C6-C 20 aryl group, or C1-C which is substituted or unsubstituted with any combination thereof 30 alkyl group, C1-C 30 halogenated alkyl group, C3-C 30 cycloalkyl group, C2-C 30 alkenyl group, C3-C 30 cycloalkenyl group, C3-C 30 heterocycloalkenyl group, C2-C 30 alkynyl group, C6-C 30 aryl group, C7-C 30 arylalkyl group, C1-C 30 heteroaryl group, and C2-C 30 heteroarylalkyl group; selected from

[0065] More specifically, in Formula 1 above, X1 and X 14 are each independently hydrogen; deuterium; and deuterium, halogen, or C1-C which is substituted or unsubstituted with any combination thereof 30 alkyl group, C3-C 30 cycloalkyl group, C2-C 30 alkenyl group, C3-C 30 cycloalkenyl group, C2-C 30 alkynyl group, and C6-C 30 aryl group; selected from

[0066] In particular, in Formula 1 above, X1 and X 14is independently selected from hydrogen; deuterium; and methyl, ethyl, phenyl, naphthyl, or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, cyclopentyl, cyclohexyl, ethenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, ethynyl, phenyl, and naphthyl group, which may be substituted or unsubstituted with deuterium, halogen, methyl, ethyl, phenyl, naphthyl, or any combination thereof.

[0067] In one embodiment, the organometallic compound is represented by any one of the following chemical formulas 1-1 to 1-4 ([Chemical Formula 1-1] to [Chemical Formula 1-4]):

Chemical Formula

[0068] In the chemical formulas 1-1 to 1-4, M 11 is the same as defined in Chemical Formula 1 above, L 11 ~L 14 each independently refers to the description related to L1 in Chemical Formula 1 above, a11 to a14 each independently refer to the description related to a1 in Chemical Formula 1 above, R 11 ~R 14 each independently refers to the description related to R1 in Chemical Formula 1 above, b11 to b14 each independently refer to the description related to b1 in Chemical Formula 1 above, Y 11 ~Y 13 each independently refers to the description related to Y1 in Chemical Formula 1 above, X 11 ~X 14 each independently refers to the description related to X1 in Chemical Formula 1 above.

[0069] In another embodiment, the organometallic compound is represented by any one of the chemical formulas 1-1 to 1-3.

[0070] In still other embodiments, the organometallic compound represented by Chemical Formula 1 is selected from the following Group I: <Group I> [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical Formula] [Chemical Formula]

[0071] In Group I, n is an integer from 1 to 4.

[0072] For example, in Chemical Formula 2, A 21 is selected from a single bond, a substituted or unsubstituted carbon atom, and a (p + q)-valent bonding unit containing at least one of a substituted or unsubstituted carbon atom and a substituted or unsubstituted benzene as a repeating unit.

[0073] Specifically, in Chemical Formula 2, A 21 is selected from a single bond, a substituted or unsubstituted carbon atom, and a (p + q)-valent bonding unit represented by any one of the following Chemical Formulas 4-1 to 4-21: [Chemical Formula] [Chemical formula] [Chemical formula]

[0074] In the above chemical formulas 4-1 to 4-21, any hydrogen may be replaced by p [Chemical formula] , q [Chemical formula] , and may be optionally substituted by any substituent.

[0075] More specifically, in the above chemical formula 2, A 21 is selected from the above chemical formula 4-8.

[0076] For example, in the above chemical formula 2, L 21 ~L 23 are each independently a single bond, O, S, CO, CO2, CR a R b , or any combination thereof, R a and R b are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, or a C1-C 10 linear, branched or cyclic monovalent hydrocarbon group which may optionally contain a heteroatom.

[0077] Specifically, in the above chemical formula 2, L 21 ~L 23 are each independently a single bond, O, CO, CO2, CR a R b , or any combination thereof, R a and R b are each independently hydrogen, deuterium, F, or a C1-C which may optionally contain F10 is a linear or branched monovalent hydrocarbon group.

[0078] For example, in the chemical formula 2, R 21 and R 22 are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group, substituted or unsubstituted C1-C 30 alkyl group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C2-C 30 alkenyl group, substituted or unsubstituted C3-C 30 cycloalkenyl group, substituted or unsubstituted C2-C 30 alkynyl group, or substituted or unsubstituted C6-C 30 aryl group.

[0079] Specifically, in the chemical formula 2, R 21 and R 22 are each independently hydrogen, deuterium, halogen, hydroxyl group, cyano group, nitro group; and deuterium, halogen, hydroxyl group, cyano group, nitro group, amino group, carbonyl group, carboxylic acid group, ether moiety, ester moiety, sulfonic acid ester moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic acid anhydride moiety, C1-C 20 alkyl group, C1-C 20 halogenated alkyl group, C1-C 20 alkoxy group, C1-C 20 halogenated alkoxy group, C3-C 20 cycloalkyl group, C3-C 20 cycloalkoxy group, C2-C 20 alkenyl group, C6-C 20 aryl group, or a C1-C 30 alkyl group, C3-C 30 cycloalkyl group, C2-C 30 alkenyl group, C3-C 30 cycloalkenyl group, C2-C 30An alkynyl group, and C6-C 30 selected from an aryl group;

[0080] For example, in the chemical formula 2 above, X 21 is a substituted or unsubstituted C1-C 10 haloalkyl group, a substituted or unsubstituted vinyl group, and a group represented by the following chemical formula 5-1:

Chemical formula

[0081] In the chemical formula 5-1 above, X 51 is a halogen, a substituted or unsubstituted C1-C 10 haloalkyl group, or a substituted or unsubstituted vinyl group, n51 is an integer from 1 to 5, R 51 is hydrogen, deuterium, a halogen, a hydroxyl group, a substituted or unsubstituted C1-C 10 haloalkyl group, or a substituted or unsubstituted vinyl group, b51 is an integer from 0 to 4, * is the bonding site with an adjacent atom.

[0082] Specifically, in the chemical formula 2 above, X 21 is represented by the following chemical formula 5-11:

Chemical formula

[0083] In one embodiment, the additive represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1:

Chem.

[0084] For example, in Chemical Formula 2-1, R z is (L 22 ) a22 -(X 21 ) o .

[0085] In one embodiment, the additive represented by Chemical Formula 2 is selected from the following Group II: <Group II>

Chem.

[0086] The additive can react with the radicals generated from the organometallic compound to form crosslinks. Therefore, the resist composition containing the additive will have improved photosensitivity, stability and / or coating properties compared to the resist composition not containing the additive.

[0087] In particular, the resist composition containing the additive can have an appropriate shelf life for commercial distribution.

[0088] The organometallic compound may be any one of those represented by the chemical formula 1, or two or more thereof may be mixed and used.

[0089] Similarly, the additive may be any one of those represented by the chemical formula 2, or two or more thereof may be mixed and used.

[0090] In the resist composition, the organometallic compound is 0.01 to 100 parts by weight, specifically 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, or 80 or less parts by weight with respect to 100 parts by weight of the resist composition. If the above range is satisfied, while the chemical bond between the organometallic compounds is not fully formed, side reactions can be suppressed, and a resist composition with improved sensitivity and / or resolution can be provided.

[0091] In the resist composition, the additive is 0.01 to 100 parts by weight, specifically 0.2 or more, 0.5 or more, 1 or more, 1.5 or more, 90 or less, or 80 or less parts by weight with respect to 100 parts by weight of the resist composition. If the above range is satisfied, while the chemical bond between the organometallic compounds is not fully formed, side reactions can be suppressed, and a resist composition with improved sensitivity and / or resolution can be provided, and the solubility of the organometallic compound can be improved.

[0092] In the resist composition, the additive is contained in an amount of 0.1 to 100,000 parts by weight with respect to 100 parts by weight of the organometallic compound. Specifically, the additive is contained in an amount of 5 to 100 parts by weight, more specifically 10 to 20 parts by weight with respect to 100 parts by weight of the organometallic compound. If the above range is satisfied, the photosensitivity, stability, and / or coating properties of the resist composition can be improved.

[0093] Upon exposure to high-energy radiation, the solubility of the resist composition in a developer changes. The resist composition is also a negative-type resist composition in which the unexposed portions of the resist film are dissolved and removed to form a negative-type resist pattern.

[0094] Also, the resist composition according to one embodiment may be for an alkali development process that uses an alkali developer in the development process during resist pattern formation, or may be for a solvent development process that uses a developer containing an organic solvent (hereinafter also referred to as an organic developer) in the development process.

[0095] Since the resist composition is non-chemically amplified, it substantially does not contain a photoacid generator.

[0096] Since the physical properties of the organometallic compound in the resist composition change upon exposure, it substantially does not contain a compound having a molecular weight of 1,000 or more other than the organometallic compound and the additive.

[0097] The organometallic compound and the additive can be produced by any suitable method or commercially available products can also be used.

[0098] The structure (composition) of the organometallic compound can be confirmed by performing FT-IR analysis, NMR analysis, fluorescent X-ray (XRF) analysis, mass spectrometry, UV analysis, single crystal X-ray structure analysis, powder X-ray diffraction (PXRD) analysis, liquid chromatography (LC) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. The detailed confirmation method is as described in the examples.

[0099] <Organic solvent> The resist composition may further contain an organic solvent.

[0100] The organic solvent contained in the resist composition is not particularly limited as long as it can dissolve or disperse the organometallic compound, additives, and optional components that may be contained as necessary. One type of the organic solvent may be used, or two or more different types may be combined and used.

[0101] In one embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or any combination thereof.

[0102] In another embodiment, the organic solvent may be a mixture of an aprotic organic solvent and a protic organic solvent.

[0103] Since the resist composition substantially does not contain water, the organic solvent does not contain water. Specifically, the resist composition contains 3% by weight or less of water, and the organic solvent contains 3% by weight or less of water.

[0104] Examples of the organic solvent include, for example, alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, sulfoxide solvents, hydrocarbon solvents, and the like.

[0105] More specifically, examples of the alcohol-based solvents include monoalcohol-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-ethylbutanol, 4-methyl-2-pentanol (MIBC), sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol; polyhydric alcohol-based solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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, tripropylene glycol;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, and other polyhydric alcohol-containing ether solvents are included.;

[0106] Examples of ether 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 tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole, among others.

[0107] Examples of ketone solvents include chain 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 2,4-pentanedione, acetonylacetone, and acetophenone, among others.

[0108] Examples of the amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone and N-methyl-2-pyrrolidone; and chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide.

[0109] Examples of ester solvents include acetate ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, t-butyl acetate, n-pentyl acetate, isopentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate; polyhydric alcohol-containing ether carboxylate 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 (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone, δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate; and glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc.

[0110] Examples of sulfoxide solvents include dimethyl sulfoxide, diethyl sulfoxide, etc.

[0111] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene.

[0112] Specifically, the organic solvent is selected from alcohol solvents, ketone solvents, ester solvents, and any combination thereof. More specifically, the organic solvent is selected from 4-methyl-2-pentanol (MIBC), propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, and any combination thereof.

[0113] The organic solvent is contained in an amount of 0 to 99.9 parts by weight based on 100 parts by weight of the resist composition. One type of the organic solvent may be used, or two or more different types may be mixed and used.

[0114] <Optional component> The resist composition may further contain a surfactant, a crosslinking agent, a leveling agent, a coloring agent, or any combination thereof, if necessary.

[0115] The resist composition may further contain a surfactant in order to improve coating properties, developability, etc. Specific examples of the surfactant include, for example, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. As the surfactant, a commercially available product or a synthetic product may be used. Examples of commercially available products of the surfactant include, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW No.75 and POLYFLOW No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), FTOP EF301, FTOP EF303, and FTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE (registered trademark) F171, MEGAFACE F173, R40, R41, and R43 (manufactured by DIC Corporation), Fluorad (registered trademark) FC430 and Fluorad FC431 (manufactured by 3M), AsahiGuard AG710 (manufactured by AGC Inc.), Surflon (registered trademark) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, and Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.).

[0116] The surfactant is contained in an amount of 0 to 20 parts by weight based on 100 parts by weight of the resist composition. One type of the surfactant may be used, or two or more different types may be mixed and used.

[0117] The method for producing the resist composition is not particularly limited. For example, a method of mixing a polymer and optional components added as necessary in an organic solvent can be used. The temperature and time during mixing are not particularly limited. If necessary, filtration can be performed after mixing.

[0118] [Pattern formation method] Hereinafter, with reference to FIGS. 1 and 2A to 2C, a pattern formation method according to an exemplary embodiment will be described in more detail. FIG. 1 is a flowchart showing a pattern formation method according to an exemplary embodiment, and FIGS. 2A to 2C are side sectional views showing a pattern formation method according to an exemplary embodiment. Hereinafter, a pattern formation method using a negative resist composition will be specifically described as an example, but it is not limited thereto.

[0119] Referring to FIG. 1, the pattern formation method includes a step (S101) of applying a resist composition onto a substrate to form a resist film, a step (S102) of exposing at least a part of the resist film with high energy rays, and a step (S103) of developing the exposed resist film using a developer. The above steps can be omitted as necessary and can also be performed in a changed order.

[0120] First, a substrate 100 is prepared. The substrate 100 can be, for example, a semiconductor substrate such as a silicon substrate or a germanium substrate, or can use glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 can also contain group III-V compounds such as GaP, GaAs, and GaSb.

[0121] The resist composition can be applied to the substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, heating (pre-bake (PB)) can also be performed to remove the organic solvent remaining in the resist film 110. Alternatively, by heating the resist film 110, radicals can be generated, and thereafter, the radicals can be chemically bonded by exposure to form a crosslink.

[0122] Coating methods can use spin coating, dipping, roller coating, or other common coating methods. Among them, spin coating can be particularly used, and the viscosity, concentration, and / or spin speed of the resist composition can be adjusted to form a resist film 110 with a desired thickness. Specifically, the thickness of the resist film 110 is 10 nm to 300 nm. More specifically, the thickness of the resist film 110 is 30 nm to 200 nm.

[0123] The lower limit of the pre-baking temperature is 60 °C or higher, specifically 80 °C or higher. Also, the upper limit of the pre-baking temperature is 150 °C or lower, specifically 140 °C or lower. The lower limit of the pre-baking time is 5 seconds or longer, specifically 10 seconds or longer. The upper limit of the pre-baking time is 600 seconds or shorter, specifically 300 seconds or shorter.

[0124] Before applying the resist composition to the substrate 100, an etching target film (not shown) can be further formed on the substrate 100. The etching target film means a layer where an image is transferred from the resist pattern and converted into a predetermined pattern. In one embodiment, the etching target film can be formed to include an insulating material such as, for example, silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the etching target film can be formed to include a conductive material such as a metal, metal nitride, metal silicide, or metal silicide nitride. In some embodiments, the etching target film can be formed to include a semiconductor material such as polysilicon. In one embodiment, an antireflection film can be further formed on the substrate 100 so as to maximize the efficiency of the resist. The antireflection film is an organic or inorganic antireflection film.

[0125] In one embodiment, in order to reduce the influence of alkaline impurities and the like contained in the process, a protective film can be further provided on the resist film 100. Further, when performing immersion exposure, in order to avoid direct contact between the immersion medium and the resist film 100, for example, an immersion protective film can be provided on the resist film 100.

[0126] Next, at least a part of the resist film 110 can be exposed with high-energy rays. For example, the high-energy rays that have passed through the mask 120 are irradiated onto at least a part of the resist film 110. As a result, the resist film 110 can have an exposed portion 111 and an unexposed portion 112.

[0127] Although not limited to a specific theory, radicals are generated in the exposed portion 111 by exposure, chemical bonds are formed between the radicals, and the physical properties of the resist composition may change.

[0128] In some cases, the exposure is performed by irradiating high-energy rays through a mask having a predetermined pattern using a liquid such as water as a medium. Examples of the high-energy rays include electromagnetic waves such as ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV, wavelength 13.5 nm), X-rays, and γ-rays; charged particle beams such as electron beams (EB) and α-rays. Irradiating these high-energy rays is collectively referred to as "exposure".

[0129] As the exposure light source, various light sources can be used, such as those that emit laser light in the ultraviolet region, such as a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and an F2 excimer laser (wavelength 157 nm); those that convert the laser light from a solid laser light source (such as a YAG or semiconductor laser) into harmonic laser light in the far ultraviolet region or vacuum ultraviolet region and emit it; those that irradiate electron beams or extreme ultraviolet rays (EUV). During exposure, usually, exposure is performed through a mask corresponding to a desired pattern. However, when the exposure light source is an electron beam, exposure can also be performed by direct drawing without using a mask.

[0130] The integrated dose of high-energy rays, for example, when extreme ultraviolet rays are used as the high-energy rays, the integrated dose is 2000 mJ / cm 2 Specifically, it is 500 mJ / cm or less as follows. Also, when electron beams are used as the high-energy rays, the integrated dose is 5000 μC / cm 2 Specifically, it is 1000 μC / cm or less as follows. 2 2

[0131]

[0132]

[0133] Subsequently, the exposed resist film 110 can be developed using a developer. The unexposed portion 112 is washed away and removed by the developer, and the exposed portion 111 remains without being washed away by the developer.

[0134] Examples of the developer include an alkaline developer and a developer containing an organic solvent (hereinafter also referred to as an "organic developer"). Examples of the developing method include a dipping method, a paddle method, a spray method, and a dynamic dosing method. The developing temperature is, for example, 5°C or higher and 60°C or lower, and the developing time is, for example, 5 seconds or longer and 300 seconds or shorter.

[0134] Examples of the alkaline developer include an alkaline aqueous solution in which one or more alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous 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 contain a surfactant.

[0135] The lower limit of the content of the alkaline compound in the alkaline developer is 0.1% by weight or more, specifically 0.5% by weight or more, and more specifically 1% by weight or more. The upper limit of the content of the alkaline compound in the alkaline developer is 20% by weight or less, specifically 10% by weight or less, and more specifically 5% by weight or less.

[0136] As the organic solvent contained in the organic developer, for example, the same organic solvents as those exemplified in the <organic solvent> part of the [resist composition] can be used. Specifically, as the organic developer, nBA (n-butyl acetate), PGME (propylene glycol methyl ether), PGMEA (propylene glycol methyl ether acetate), GBL (γ-butyrolactone), IPA (isopropanol), etc. are used. The organic developer may further contain organic acids such as acetic acid, formic acid, and citric acid.

[0137] The lower limit of the content of the organic solvent in the organic developer is 80% by weight or more, specifically 90% by weight or more, more specifically 95% by weight or more, and particularly 99% by weight or more.

[0138] The organic developer may contain a surfactant. The organic developer may also contain a trace amount of water. Also, during development, development can be stopped by substituting with a solvent of a different type from the organic developer.

[0139] The developed resist pattern can be further cleaned. As the cleaning liquid, ultrapure water, a rinsing liquid, etc. can be used. As the rinsing liquid, as long as it does not dissolve the resist pattern, there is no particular limitation, and a solution containing a general organic solvent can be used. For example, the rinsing liquid may be an alcohol-based solvent or an ester-based solvent. After cleaning, the rinsing liquid remaining on the substrate and the pattern can be removed. Also, when ultrapure water is used, the water remaining on the substrate and the pattern can be removed.

[0140] Also, the developer can be used alone or in combination of two or more.

[0141] After forming the resist pattern as described above, by etching, a patterned wiring substrate can be obtained. The etching method is carried out by a known method such as dry etching using a plasma gas and wet etching using an alkaline solution, a cupric chloride solution, a ferric chloride solution, etc.

[0142] After forming the resist pattern, plating can also be carried out. The plating method is not particularly limited, but for example, there are copper plating, solder plating, nickel plating, gold plating, etc.

[0143] The remaining resist pattern after etching can be peeled off with an organic solvent. Examples of such organic solvents are not particularly limited, but for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), etc. can be mentioned. The peeling method is not particularly limited, but for example, the dipping method, the spraying method, etc. can be mentioned. Also, the wiring substrate on which the resist pattern is formed is also a multilayer wiring substrate and can also have small-diameter through holes.

[0144] In one embodiment, the wiring board can also be formed by a method in which, after forming a resist pattern, metal is vapor-deposited in a vacuum and then the resist pattern is dissolved in a solution, that is, a lift-off method.

[0145] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited only to the following examples.

Example

[0146] Synthesis Example 1: Synthesis of T1

Chemical formula

[0147] 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 then the temperature was raised to 90°C. After adding about 1.0 ml of DI water, 10.0 g (69.2 mmol) of 4-fluorobenzyl chloride was added dropwise over 10 minutes. After heating under reflux and stirring at 130°C for 4 hours, unreacted Sn powder was filtered using a Buchner funnel. At the same time, while the filtered solution was cooled, 6.5 g (yield 36%) of white crystals (T1 precursor), which were the product, were obtained.

[0148]

Chemical formula

[0149] 1.5 g (3.7 mmol) of T1 precursor and 21.0 ml of dry acetone were placed in a 50 ml single-necked flask, and then the temperature was lowered to 0°C. After adding 0.6 g (7.4 mmol) of sodium acetate, the mixture was stirred for about 12 hours. The generated NaCl salt in the solution was filtered using a 0.45 μm filter, and the filtered solution was concentrated by rotary evaporation and dried under vacuum to obtain 1.6 g of T1 (yield 74%). 1H-NMR (500 MHz, DMSO-d6): δ ~6.9 (8H), ~2.6 (4H), ~1.6 (6H)

[0150] Synthesis Example 2: Synthesis of T2

Chem.

[0151] T1 precursor (4.0 g, 9.81 mmol) was placed in a round-bottom flask and purged with N2. After diluting with acetone (98 ml, 0.1 M), sodium propionate (1.88 g, 19.6 mmol) was added at 0 °C. After reacting at 0 °C for 16 hours, it was filtered using celite. After removing the solvent, recrystallization (dichloromethane: n-hexane = 10 ml: 100 ml) was performed. After filtration, it was dried under vacuum to obtain T2 (3.7 g, 79%). 1 H NMR (500 MHz, CD2Cl2) δ 7.18 - 6.72 (m, 8H), 2.96 (s, 4H), 2.17 (q, J = 7.6 Hz, 4H), 1.00 (t, J = 7.6 Hz, 6H). 13 C NMR (126 MHz, CD2Cl2) δ 185.28, 161.41 (d, J = 243.4 Hz), 132.47 (d, J = 3.2 Hz), 130.34 (d, J = 7.9 Hz), 115.44 (d, J = 21.6 Hz), 31.23, 27.36, 9.69. 119 Sn NMR (186 MHz, CD2Cl2) δ -251.42 (t, J = 48.9 Hz).

[0152] Synthesis Example 3: Synthesis of T3

Chem.

[0153] (1) Synthesis of T3-2 Fluorene (8.31 g, 50.0 mmol) was placed in an N₂ - replaced two - necked round - bottom flask and diluted with THF (30 ml). After dropwise addition of n - BuLi (2.5 M in hexane, 20 ml, 50 mmol) at - 78 °C, the mixture was stirred at 0 °C for 0.5 h. Dichlorodiphenylstannane (8.60 g, 25.0 mmol) was placed in a vial and diluted with Et₂O (diethyl ether) (50 ml, total Et₂O 100 ml (0.25 M)). The solution in the vial was dropwise added to the round - bottom flask at - 78 °C. After stirring for 0.5 h, the temperature was raised to room temperature and stirred for another 0.5 h. After confirming the completion of the reaction, the solvent was removed, filtered through silica / celite, and purified by column chromatography (dichloromethane (DCM): n - hexane (DCM 10 v%)) to obtain T3 - 2 (12.1 g, 80%). 1 ¹H NMR (500 MHz, CD₂Cl₂) δ 7.88 (d, J = 7.6 Hz, 4H), 7.36 - 7.23 (m, 10H), 7.23 - 7.08 (m, 8H), 6.79 - 6.61 (m, 4H), 4.85 (s, 2H). 13 ¹³C NMR (126 MHz, CD₂Cl₂) δ 145.31, 139.91, 137.35, 137.13, 129.52, 128.51, 126.60, 125.51, 124.18, 120.54, 40.69. 119 ¹¹⁹Sn NMR (186 MHz, CD₂Cl₂) δ - 89.93.

[0154] (2) Synthesis of T3 - 1 T3 - 2 (12.0 g, 20.0 mmol) was placed in a round - bottom flask and replaced with N₂. After dilution with dichloromethane (200 ml, 0.1 M), a 2 M HCl in Et₂O solution (30 ml, 60 mmol) was dropwise added at - 78 °C. After stirring at - 78 °C for 1 h, the temperature was raised to room temperature and reacted for another 12 h. After removing the solvent, the precipitate was washed with n - hexane, and the precipitate was dried under vacuum to obtain T3 - 1 (8.8 g, 85%). 11H NMR (500 MHz, CD2Cl2) δ 7.70 (d, J = 7.6 Hz, 4H), 7.38 - 7.25 (m, 8H), 7.11 (td, J = 7.5, 1.2 Hz, 4H), 4.63 (s, 2H). 13 13C NMR (126 MHz, CD2Cl2) δ 140.34, 139.90, 127.61, 127.28, 124.49, 120.90, 50.12. 119 119Sn NMR (186 MHz, CD2Cl2) δ -26.58.

[0155] (3) Synthesis of T3 T3-1 (1.5 g, 2.88 mmol) was placed in a round-bottom flask and purged with N2. After diluting with acetone (29 ml, 0.1 M), sodium propionate (0.55 g, 5.77 mmol) was added at 0 °C. After reacting at 0 °C for 16 hours, it was filtered using celite. After removing the solvent, recrystallization (dichloromethane: n-hexane = 5 ml: 100 ml) was carried out. After filtration, it was dried under vacuum to obtain T3 (1.30 g, 76%). 1 1H NMR (500 MHz, CD2Cl2) δ 7.80 (d, J = 7.6 Hz, 4H), 7.39 - 7.26 (m, 8H), 7.17 (td, J = 7.5, 1.2 Hz, 4H), 4.52 (s, 2H), 2.04 (q, J = 7.5 Hz, 4H), 0.86 (t, J = 7.6 Hz, 6H). 13 13C NMR (126 MHz, CD2Cl2) δ 185.75, 142.17, 140.73, 126.86, 126.77, 124.87, 120.32, 51.64, 26.85, 9.47. 119 119Sn NMR (186 MHz, CD2Cl2) δ -338.11.

[0156] Production Example: Production of Casting Solution The organometallic compounds synthesized in Synthesis Examples 1 to 3 were dissolved in a casting solvent at 2% by weight to obtain casting solutions A-1 to A-3. The additives described in Table 1 below were dissolved in ethyl lactate at 2% by weight to obtain casting solutions A-4 and A-5. The organometallic compounds synthesized in Synthesis Examples 1 to 3 were dissolved in a casting solvent at 2% by weight, and the additives described in Table 1 below were further added thereto such that the weight ratio of the additive to the organometallic compound was 3:1 to obtain casting solutions B-1 to B-6. Further, the organometallic compound synthesized in Synthesis Example 1 was dissolved in a casting solvent at 2% by weight, and the additives described in Table 1 below were further added thereto such that the weight ratio of the additive to the organometallic compound was 4:1 to obtain casting solutions C-1 and C-2.

[0157]

Table 1

[0158]

Chemical formula

[0159] Evaluation Example 1: Evaluation of Surface Roughness (Rq) A silicon wafer coated with HMDS as a bottom film of 3 nm was subjected to O2 plasma treatment for 30 minutes, and then casting solutions A-1 to A-5, B-1 to B-6, C-1 and C-2 were spin-coated at 1500 rpm for 1 minute, followed by drying (PAB) at 120°C for 1 minute to produce films having the initial thicknesses shown in Table 2 below. Next, a thickness 3.5 mm jig (4×4) with rectangular holes (1 cm×1 cm) empty was placed on the films obtained using casting solutions A-1 to A-5, B-1 to B-6, C-1 and C-2, and DUV with a wavelength of 254 nm was irradiated to each hole at 60 mJ / cm 2It was exposed at a dose of and dried at 150 °C for 1 minute (PEB). The dried film was immersed in a PGMEA solution in which acetic acid was dissolved at 2 wt% as a developer at 25 °C for 60 seconds, and then the surface of the remaining film was observed through an Atomic Force Microscope, and Rq was calculated from the average value of the observed height. Next, the relative value of Rq was calculated, and the results are shown in Table 2 below. At this time, for Examples 1-1, 1-2, 1-7, and 1-8, the relative values were calculated based on Comparative Example 1-1, and for Examples 1-3 and 1-4, the relative values were calculated based on Comparative Example 1-2, and for Examples 1-4 and 1-5, the relative values were calculated based on Comparative Example 1-3.

[0160]

Table 2

[0161] Referring to Table 2 above, in Comparative Examples 1-4 and 1-5 using casting solutions A-4 and A-5 containing only the additive, no thin films were formed, and Rq could not be measured.

[0162] Referring to Table 2 above, Examples 1-1 to 1-8 containing the additive showed significantly lower Rq values compared to Comparative Examples 1-1 to 1-3, from which it can be confirmed that the coating properties of the resist composition containing the additive are improved.

[0163] Evaluation Example 2: Thin Film Development Evaluation After subjecting a silicon wafer coated with a 3 nm bottom film of HMDS to O2 plasma treatment for 30 minutes, casting solutions A-1 to A-5, B-1 to B-6, C-1, and C-2 were spin-coated at 1500 rpm for 1 minute, respectively, and then dried at 120 °C for 1 minute (PAB) to form films. Next, a 3.5 mm thick zig (4×4) with rectangular holes (1 cm × 1 cm) was placed on the films obtained using casting solutions A-1 to A-5, B-1 to B-6, C-1, and C-2, and DUV with a wavelength of 254 nm was applied to each hole at 0 to 60 mJ / cm 2It was exposed at a dose of [[ID=]], and dried at 150 °C for 1 minute (PEB). The dried film was immersed in a PGMEA solution in which acetic acid was dissolved at 2% by weight as a developer at 25 °C for 60 seconds, and then the remaining film thickness was measured and shown in Table 3 below. At this time, for Examples 2-1, 2-2, 2-7, and 2-8, relative values were calculated based on Comparative Example 2-1, and for Examples 2-3 and 2-4, relative values were calculated based on Comparative Example 2-2, and for Examples 2-4 and 2-5, relative values were calculated based on Comparative Example 2-3.

[0164]

Table 3

[0165] In Table 3 above, E th means the exposure amount at the point when the thin film starts to harden, and E1 means the exposure amount at the saturation point where the thickness of the thin film does not increase any further.

[0166] Referring to Table 3 above, in Comparative Examples 2-4 and 2-5 using casting solutions A-4 and A-5 containing only additives, no thin films were formed respectively, and E th and E1 could not be measured.

[0167] Referring to Table 3 above, it can be confirmed that E th and E1 of Examples 2-1 to 2-8 are smaller than E th and E1 of Comparative Examples 2-1 to 2-3. From this, it was confirmed that the photosensitivity is improved when using additives.

Claims

1. A resist composition comprising an organometallic compound represented by the following Chemical Formula 1 and an additive represented by the following Chemical Formula 2: In the above Chemical Formulas 1 and 2, 【Chemical 1】 n is an integer from 1 to 6, M １１ is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi), or polonium (Po), R ｘ is *-(L １ ) ａ１ -(R １ ) ｂ１ and is R ｙ is *-Y １ -X １ and m is an integer from 0 to 6, m - n is 0 or more, a1 is an integer from 1 to 4, A plurality of Rs ｘ may be the same as or different from each other A plurality of Rs ｙ may be the same as or different from each other L １ is a single bond or a linear, branched or cyclic divalent hydrocarbon group of C １ -C ３０ which may optionally contain a heteroatom, b1 is an integer from 1 to 4, R １ is a substituted or unsubstituted C １ -C ３０ alkyl group, a substituted or unsubstituted C ３ -C ３０ cycloalkyl group, a substituted or unsubstituted C ３ -C ３０ heterocycloalkyl group, a substituted or unsubstituted C ２ -C ３０ alkenyl group, a substituted or unsubstituted C ３ -C ３０ cycloalkenyl group, a substituted or unsubstituted C ３ -C ３０ heterocycloalkenyl group, a substituted or unsubstituted C ２ -C ３０ alkynyl group, a substituted or unsubstituted C ６ -C ３０ aryl group, a substituted or unsubstituted C ７ -C ３０ arylalkyl group, a substituted or unsubstituted C １ -C ３０ heteroaryl group, or a substituted or unsubstituted C ２ -C ３０ heteroarylalkyl group, and two adjacent groups among a plurality of R １ s can optionally be bonded to each other to form a fused ring. a21 to a23 are each independently an integer from 1 to 6, Y １ is O, O(C=O), S, S(C=O), NX １４ , or NX １４ (C=O), and X １ and X １４ each independently is a linear, branched or cyclic monovalent hydrocarbon group which may optionally contain hydrogen, deuterium or a heteroatom, １ -C ３０ ​ A ２１ is a single bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted silicon atom, or a (p + q)-valent bonding unit, and L ２１ to L ２３ each independently represents a single bond; O; S; CO; CO ２ ; C optionally containing a heteroatom １ -C ３０ which is a linear, branched or cyclic divalent hydrocarbon group; or any combination thereof, b21 is an integer from 1 to 4, R ２１ and R ２２ each independently represents hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, or a C １ -C ３０ linear, branched or cyclic monovalent hydrocarbon group which may optionally contain a heteroatom, b22 is an integer from 1 to 5, o is an integer from 1 to 10, X ２１ is a substituted or unsubstituted C １ -C ３０ alkyl group, a substituted or unsubstituted C １ -C ３０ haloalkyl group, a substituted or unsubstituted C ２ -C ３０ alkenyl group, or a substituted or unsubstituted C ６ -C ３０ aryl group, and p is an integer from 1 to 10, q is an integer from 0 to 10, * is a bonding site with an adjacent atom. A ２１ , L ２１ ~L ２３ , R ２１ and R ２２ adjacent two of the groups may optionally be bonded to each other to form a ring;

2.

3. M １１ The resist composition according to claim 1, wherein M is In, Sn, or Sb. The resist composition according to Claim 1, wherein n is an integer from 1 to 4 and m is an integer from 0 to 3.

4.

5.

6. L １ is a single bond, a substituted or unsubstituted C １ -C ３０ -alkylene group, a substituted or unsubstituted C ３ -C ３０ -cycloalkylene group, a substituted or unsubstituted C ３ -C ３０ -heterocycloalkylene group, a substituted or unsubstituted C ２ -C ３０ -alkenylene group, a substituted or unsubstituted C ３ -C ３０ -cycloalkenylene group, a substituted or unsubstituted C ３ -C ３０ -heterocycloalkenylene group, a substituted or unsubstituted C ６ -C ３０ -arylene group, or a substituted or unsubstituted C １ -C ３０ -heteroarylene group, the resist composition according to claim 1.

7. R １ is deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid 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 group, C １ -C ２０ halogenated alkyl group, C １ -C ２０ alkoxy group, C １ -C ２０ alkylthio group, C １ -C ２０ halogenated alkoxy group, C １ -C ２０ halogenated alkylthio group, C ３ -C ２０ cycloalkyl group, C ３ -C ２０ cycloalkoxy group, C ３ -C ２０ cycloalkylthio group, C ６ -C ２０ aryl group, C １ -C ２０ heteroaryl group, C ６ -C ２０ aryloxy group, C ６ -C ２０ arylthio group, C １ -C ２０ heteroaryloxy group, C １ -C ２０ heteroarylthio group, or C substituted or unsubstituted with any combination thereof, C １ -C ３０ alkyl group, C ３ -C ３０ cycloalkyl group, C ３ -C ３０ heterocycloalkyl group, C ２ -C ３０ alkenyl group, C ３ -C ３０ cycloalkenyl group, C ３ -C ３０ heterocycloalkenyl group, C ２ -C ３０ alkynyl group, C ６ -C ３０ aryl group, C ７ -C ３０ arylalkyl group, C １ -C ３０ heteroaryl group, and C ２ -C ３０ The resist composition according to claim 1, selected from heteroarylalkyl groups.

8. Y １ The resist composition according to claim 1, wherein Y is O, O(C=O), S, or S(C=O).

9. X １ and X １４ is, independently of one another, hydrogen; deuterium; and deuterium, halogen, cyano group, nitro group, hydroxy group, thiol group, amino group, carboxylic acid group, ether moiety, thioether moiety, carbonyl moiety, ester moiety, phosphonate moiety, sulfonate moiety, carbonate moiety, amide moiety, lactone moiety, sultone moiety, carboxylic anhydride moiety, C １ -C ２０ alkyl group, C １ -C ２０ halogenated alkyl group, C １ -C ２０ alkoxy group, C １ -C ２０ alkylthio group, C １ -C ２０ halogenated alkoxy group, C １ -C ２０ halogenated alkylthio group, C ３ -C ２０ cycloalkyl group, C ３ -C ２０ cycloalkoxy group, C ３ -C ２０ cycloalkylthio group, C ６ -C ２０ aryl group, C １ -C ２０ heteroaryl group, C ６ -C ２０ aryloxy group, C ６ -C ２０ arylthio group, C １ -C ２０ heteroaryloxy group, C １ -C ２０ heteroarylthio group, or C substituted or unsubstituted with any combination thereof, C １ -C ３０ alkyl group, C １ -C ３０ halogenated alkyl group, C １ -C ３０ alkoxy group, C １ -C ３０ alkylthio group, C １ -C ３０ Halogenated alkoxy group, C １ -C ３０ Halogenated alkylthio group, C ３ -C ３０ Cycloalkyl group, C ３ -C ３０ Cycloalkoxy group, C ３ -C ３０ Cycloalkylthio group, C ３ -C ３０ Heterocycloalkyl group, C ２ -C ３０ Alkenyl group, C ３ -C ３０ Cycloalkenyl group, C ３ -C ３０ Heterocycloalkenyl group, C ２ -C ３０ Alkynyl group, C ６ -C ３０ Aryl group, C ６ -C ３０ Aryloxy group, C ６ -C ３０ Arylthio group, C ７ -C ３０ Arylalkyl group, C １ -C ３０ Heteroaryl group, C １ -C ３０ Heteroaryloxy group, C １ -C ３０ Heteroarylthio group, and C ２ -C ３０ Heteroarylalkyl group; The resist composition according to claim 1, which is selected from.

10.

11. 【Chemical 2】

12. M １１ is the same as the definition in Chemical Formula 1 above, L １１ ~L １４ each independently has the same definition as L in Chemical Formula 1 １ and is as follows

13. R １１ ~R １４ each independently has the same definition as R in Chemical Formula 1 above, １ and is as follows. The resist composition according to Claim 1, wherein the organometallic compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4 ([Chemical Formula 1-1] to [Chemical Formula 1-4]): Y １１ ~Y １３ each independently has the same definition as Y in Chemical Formula 1 １ and is as follows X １１ to X １４ each independently has the same definition as X in Chemical Formula 1 １ above. In the above Chemical Formulas 1-1 to 1-4, a11 to a14 are each independently the same as the definition of a1 in Chemical Formula 1, b11 to b14 are each independently the same as the definition of b1 in Chemical Formula 1. 【Chemical Formula 3】 【Chemical Formula 4】 [Chemical Formula 5] [[Chemical Formula 6]] 【Chemical Formula 7】 【Chemical Formula 8】 【Chemical Formula 9】 【Chemical 10】

14. The resist composition according to Claim 1, wherein the organometallic compound represented by Chemical Formula 1 is selected from the following Group I: A ２１ is the resist composition according to claim 1, selected from a single bond, a substituted or unsubstituted carbon atom, and a (p + q)-valent bonding unit containing at least one of a substituted or unsubstituted carbon atom and a substituted or unsubstituted benzene as a repeating unit. <Group I> L ２１ to L ２３ each independently represents a single bond, O, S, CO, CO ２ CR ａ R ｂ or any combination thereof, R ａ and R ｂ each independently may optionally contain hydrogen, deuterium, halogen, a hydroxyl group, a cyano group, a nitro group, or a C １ -C １０ linear, branched or cyclic monovalent hydrocarbon group of, the resist composition according to claim 1. In the above Group I, n is an integer from 1 to 4. R ２１ and R ２２ each independently represents hydrogen, deuterium, a halogen, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted C １ -C ３０ alkyl group, a substituted or unsubstituted C ３ -C ３０ cycloalkyl group, a substituted or unsubstituted C ２ -C ３０ alkenyl group, a substituted or unsubstituted C ３ -C ３０ cycloalkenyl group, a substituted or unsubstituted C ２ -C ３０ alkynyl group, or a substituted or unsubstituted C ６ -C ３０ aryl group, the resist composition according to claim 1.

15. X ２１ is a substituted or unsubstituted C １ -C １０ haloalkyl group, a substituted or unsubstituted vinyl group, and a group represented by the following Chemical Formula 5-1, the resist composition according to claim 1: 【Chemical 11】

16. X ５１ is a halogen, a substituted or unsubstituted C １ -C １０ haloalkyl group, or a substituted or unsubstituted vinyl group,

17. R ５１ is hydrogen, deuterium, a halogen, a hydroxyl group, a substituted or unsubstituted C １ -C １０ haloalkyl group, or a substituted or unsubstituted vinyl group,

18.

19. In the above Chemical Formula 5-1, n51 is an integer from 1 to 5, 【Chemical 12】 b51 is an integer from 0 to 4, R ｚ is selected from R ２２ and (L ２２ ) ａ２２ -(X ２１ ) ｏ and at least one of R ｚ is (L ２２ ) ａ２２ -(X ２１ ) ｏ and R ２２ to R ２９ each independently has the same definition as R in Chemical Formula 2 ２２ and is as follows * is a bonding site with an adjacent atom.

20. The resist composition according to Claim 1, wherein the additive represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1: In the above Chemical Formula 2-1, 【Chemical 13】 b27 to b29 are each independently an integer from 1 to 4.

21. The resist composition according to Claim 1, wherein the additive is contained in an amount of 0.1 to 100,000 parts by weight based on 100 parts by weight of the organometallic compound.

22. Coating the resist composition according to any one of Claims 1 to 16 on a substrate to form a resist film; Exposing at least a part of the resist film with high-energy rays; Developing the exposed resist film using a developer, the method for forming a pattern including the steps.

18. The method for forming a pattern according to claim 17, wherein the exposing step is performed by irradiating far ultraviolet rays (DUV), extreme ultraviolet rays (EUV) and / or electron beams (EB).

19. The method for forming a pattern according to claim 17, wherein the organometallic compound undergoes a crosslinking reaction by exposing the resist film.

20. The exposed resist film includes an exposed portion and an unexposed portion, In the developing step, the unexposed portion is removed, the method for forming a pattern according to claim 17.

Images