Resist composition and pattern forming method using the same

Abstract

To provide a resist composition and a pattern forming method using the resist composition.SOLUTION: There are provided: a resist composition which contains an organometallic compound of a specific structure having indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi) or polonium (Po), and an additive of a specific structure having a single bond, a double bond or a C1-C30 linear, branched or cyclic divalent hydrocarbon group or the like; and a pattern production method using the resist composition.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resist composition and a pattern forming method utilizing the resist composition. [Background technology]

[0002] In the manufacture of conductors, resists whose physical properties change in response to light are used to form fine patterns. Among them, chemically amplified resists have been widely used. In chemically amplified resists, an acid formed by the reaction of light with a photoacid generator further reacts with a base resin, changing the solubility of the base resin in a developer, thereby enabling patterning.

[0003] However, in the case of chemically amplified resists, the acid formed can diffuse into unexposed areas, causing problems such as poor pattern uniformity or increased surface roughness. In addition, as semiconductor processes become increasingly miniaturized, it is no longer easy to control the diffusion of acid, making it necessary to develop a new type of resist.

[0004] Recently, in order to overcome the limitations of chemically amplified resists, attempts have been made to develop materials whose physical properties change upon exposure, but the problem of the high dose required for exposure remains. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide a resist composition that has improved storage stability, changes physical properties even upon exposure to low doses, and provides a pattern with improved resolution, and a method for forming a pattern using the resist composition. [Means for solving the problem]

[0006] According to one embodiment, there is provided a resist composition comprising an organometallic compound represented by any one of the following formulas 1-1 to 1-4 and an additive represented by the following formula 2: [ka] In the above Chemical Formulae 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 Or L 14 are each independently a single bond or a C1-C30 linear, branched or cyclic divalent hydrocarbon group; a11 to a14 are each independently selected from integers of 1 to 4; R 11 Or R 14 each independently represents a substituted or unsubstituted C 3 -C 30 Branched alkyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl groups, substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl groups, substituted or unsubstituted C 6 -C 30 Aryl groups, substituted or unsubstituted C 7 -C 30 Arylalkyl groups, substituted or unsubstituted C 1 -C 30 Heteroaryl groups, or substituted or unsubstituted C 2 -C 30is a heteroarylalkyl group, R 11 Or R 14 adjacent two of may be optionally bonded to each other to form a fused ring; b11 to b14 are each independently selected from integers of 1 to 4; Y 11 Or Y 13 are each independently O, O(C=O), S, S(C=O), NX14 or N(C=O); X 11 Or X 14 each independently represents a C which may optionally contain hydrogen, deuterium, or heteroatoms; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of Y 21 and Y 22 each independently represents a C having one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of L 21 is a single bond, a double bond, or C 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of Each a21 is independently selected from an integer of 1 to 4; Y 21 , Y 22 and L 21 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0007] According to another embodiment, there is provided a pattern forming method including the steps of applying the resist composition described above to form a resist film, exposing at least a portion of the resist film to high-energy radiation, and developing the exposed resist film using a developer. Effect of the Invention

[0008] The present invention can provide a resist composition that has improved storage stability and improved sensitivity, providing patterns with improved resolution. [Brief description of the drawings]

[0009] [Figure 1] 1 is a flowchart illustrating a pattern forming method according to an embodiment of the present invention. [Figure 2A] 1A to 1C are side cross-sectional views illustrating a pattern forming method according to an embodiment of the present invention. [Figure 2B] 1A to 1C are side cross-sectional views illustrating a pattern forming method according to an embodiment of the present invention. [Figure 2C] 1A to 1C are side cross-sectional views illustrating a pattern forming method according to an embodiment of the present invention. [Figure 3A] FIG. 13 is a graph showing the change in film thickness after development depending on the dose in Comparative Example 3-1. [Figure 3B] 1 is a graph showing a change in film thickness after development depending on the dose in Example 3-1. [Figure 4A] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4B] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4C] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4D] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 4E] 1A-1D are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention. [Figure 5A] 1A-1D are side cross-sectional views illustrating a method of forming a semiconductor device according to one embodiment of the present invention. [Figure 5B] 1A-1D are side cross-sectional views illustrating a method of forming a semiconductor device according to one embodiment of the present invention. [Figure 5C] 1A-1D are side cross-sectional views illustrating a method of forming a semiconductor device according to one embodiment of the present invention. [Figure 5D] 1A-1D are side cross-sectional views illustrating a method of forming a semiconductor device according to one embodiment of the present invention. [Figure 5E] 1A-1D are side cross-sectional views illustrating a method of forming a semiconductor device according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention can be modified in various ways and has various embodiments, but specific embodiments are illustrated in the drawings and described in detail in the detailed description. However, they do not limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, or alternatives within the spirit and technical scope of the present invention. In the description of the present invention, if it is determined that a detailed description of related publicly known technology would not make the gist of the present invention unclear, the detailed description will be omitted.

[0011] Terms such as "first," "second," and "third" may be used to describe various components, but are used only for the purpose of distinguishing one component from other components and do not limit the order, types, etc. of the components.

[0012] In this specification, when a part such as a layer, film, region, or plate is described as being "on" or "above" another part, it does not only mean that it is in contact with another part and is directly above, below, or to the left or right, but also includes a part that is not in contact with another part and is directly above, below, or to the left or right.

[0013] The singular term includes the plural term unless the context clearly indicates otherwise. Terms such as "comprise" or "have" are to be understood as indicating the presence of a feature, number, step, operation, component, part, ingredient, material, or combination thereof described in the specification, unless specifically 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, ingredients, materials, or combinations thereof.

[0014] Whenever a range of values ​​is recited, the range includes all values ​​that fall within the range, as expressly recorded, and includes the boundaries of the range in addition, so a range "from X to Y" includes all values ​​between X and Y, including X and Y.

[0015] In this specification, "C x -C y " means that the number of carbon atoms constituting the substituent is x to y. For example, "C 1 -C 6 " means that the number of carbon atoms constituting the substituent is 1 to 6, and "C 6 -C 20 " means that the number of carbon atoms constituting the substituent is 6 to 20.

[0016] In this specification, the term "monovalent hydrocarbon group" refers to a monovalent residue derived from an organic compound containing carbon and hydrogen or a derivative thereof, and specific examples thereof include linear or branched alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, and nonyl groups); monovalent saturated cyclic aliphatic hydrocarbon groups (cycloalkyl groups) (e.g., cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl, tetracyclododecanylmethyl and dicyclohexylmethyl groups; monovalent unsaturated aliphatic hydrocarbon groups (alkenyl and alkynyl groups) (e.g., allyl groups); monovalent unsaturated cyclic aliphatic hydrocarbon groups (cycloalkenyl groups) (e.g., 3-cyclohexenyl groups); aryl groups (e.g., phenyl, 1-naphthyl and 2-naphthyl groups); arylalkyl groups (e.g., benzyl and diphenylmethyl groups); heteroatom-containing monovalent hydrocarbon groups (e.g., tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl and 3-oxocyclohexyl groups), or any combination thereof.In addition, in these groups, some of the hydrogens may be replaced by moieties containing heteroatoms, such as oxygen, sulfur, nitrogen, phosphorus or halogen atoms, or some of the carbons may be replaced by moieties containing heteroatoms, such as oxygen, sulfur, nitrogen or phosphorus, so that these groups may contain a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, or the like.

[0017] In the present specification, the term "divalent hydrocarbon group" refers to a divalent residue in which any one hydrogen atom of a monovalent hydrocarbon group is replaced at 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 cycloalkylene group, an arylene group, or groups in which some carbon atoms of these groups are replaced with heteroatoms.

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

[0019] In the present specification, the term "halogenated alkyl group" refers to a group in which one or more substituents of an alkyl group are substituted with halogen. Specific examples include CF 3 etc., where halogen is F, Cl, Br or I.

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

[0021] As used herein, an "alkylthio group" is defined as -SA 101 where A means a monovalent group having the formula 101は、 It is an alkyl group.

[0022] In the present specification, the term "halogenated alkoxy group" refers to an alkoxy group in which one or more hydrogen atoms are replaced with halogen. A specific example is -OCF 3 etc.

[0023] As used herein, the term "halogenated alkylthio group" refers to an alkylthio group in which one or more hydrogen atoms are replaced with halogen. Specific examples include -SCF 3 etc.

[0024] In this specification, a "cycloalkyl group" means a monovalent saturated hydrocarbon ring 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 polycyclic fused ring groups such as a norbornyl group and an adamantyl group.

[0025] In this specification, a "cycloalkylene group" means a divalent saturated hydrocarbon ring 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.

[0026] As used herein, a "cycloalkoxy group" is defined as -OA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group. Specific examples thereof include a cyclopropoxy group, a cyclobutoxy group, and the like.

[0027] As used herein, a "cycloalkylthio group" is defined as -SA 102 where A means a monovalent group having the formula 102 is a cycloalkyl group.

[0028] As used herein, a "heterocycloalkyl group" refers to a cycloalkyl group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen, and the heterocycloalkyl group may specifically contain an ether bond, an ester bond, a sulfonate ester bond, a carbonate, a lactone ring, a sultone ring, or a carboxylic anhydride moiety. As used herein, a "heterocycloalkylene group" refers to a cycloalkylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0029] As used herein, a "heterocycloalkoxy group" is defined as -OA 103 where A means a monovalent group having the formula 103 is a heterocycloalkyl group.

[0030] As used herein, a "heterocycloalkylthio group" is defined as -SA 103 where A means a monovalent group having the formula 103 is a heterocycloalkyl group.

[0031] As used herein, an "alkenyl group" refers to a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon double bonds. As used herein, an "alkenylene group" refers to a linear or branched, unsaturated aliphatic hydrocarbon divalent group containing one or more carbon-carbon double bonds.

[0032] As used herein, a "cycloalkenyl group" refers to a monovalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds. As used herein, a "cycloalkenylene group" refers to a divalent unsaturated hydrocarbon ring group containing one or more carbon-carbon double bonds.

[0033] As used herein, a "heterocycloalkenyl group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen. As used herein, a "heterocycloalkenylene group" refers to a cycloalkenylene group in which some of the carbon atoms are replaced by a moiety containing a heteroatom, such as oxygen, sulfur, or nitrogen.

[0034] As used herein, the term "alkynyl group" means a linear or branched, unsaturated aliphatic hydrocarbon monovalent group containing one or more carbon-carbon triple bonds.

[0035] As used herein, an "aryl group" refers to a monovalent group having a carbocyclic aromatic system, and specific examples include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, etc. As used herein, an "arylene group" refers to a divalent group having a carbocyclic aromatic system.

[0036] As used herein, an "aryloxy group" is -OA 104 where A means a monovalent group having the formula 104 is an aryl group.

[0037] As used herein, an "arylthio group" is defined as -SA 104 where A means a monovalent group having the formula 104 is an aryl group.

[0038] As used herein, a "heteroaryl group" refers to a monovalent group having a heterocyclic aromatic system, and specific examples include pyridinyl groups, pyrimidinyl groups, pyrazinyl groups, etc. As used herein, a "heteroarylene group" refers to a divalent group having a heterocyclic aromatic system.

[0039] As used herein, a "heteroaryloxy group" is defined as -OA 105 where A means a monovalent group having the formula 105is a heteroaryl group.

[0040] As used herein, a "heteroarylthio group" is defined as -SA 105 where A means a monovalent group having the formula 105 is a heteroaryl group.

[0041] As used herein, "arylalkyl group" refers to an alkyl group substituted with a monovalent group having a carbocyclic aromatic system, and specific examples include a benzyl group, a diphenylmethyl group, and the like.

[0042] As used herein, "heteroarylalkyl group" refers to an alkyl group substituted with a monovalent group having a heterocyclic aromatic system. In the present specification, the term "heterocyclic group" refers to a monocyclic or polycyclic group having 1 to 60 carbon atoms containing at least one heteroatom, and includes monovalent, divalent, trivalent and other groups.

[0043] In this specification, the term "substituent" means deuterium, halogen, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group or C 1 -C 20 Heteroarylthio groups; 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 groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group, C 1 -C20 C substituted with heteroarylthio groups, or any combination thereof 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryl groups, C 1 -C 20 Heteroaryloxy group or C 1 -C 20 heteroarylthio groups; and any combination thereof.

[0044] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the description with reference to the drawings, substantially the same or corresponding components are given the same drawing numbers, and duplicate descriptions related thereto will be omitted. In the drawings, thicknesses are shown enlarged to clearly express various layers and regions. In addition, in the drawings, thicknesses of some layers and regions are shown exaggerated for convenience of explanation. Note that the embodiments described below are merely illustrative, and various modifications are possible from such embodiments.

[0045] [Resist composition] The resist composition according to the exemplary embodiment includes an organometallic compound represented by any one of the following formulas 1-1 to 1-4; and an additive represented by the following formula 2: [ka] In Chemical Formulae 1-1 to 1-4 and Chemical Formula 2, M 11 is indium (In), tin (Sn), antimony (Sb), tellurium (Te), thallium (Tl), lead (Pb), bismuth (Bi) or polonium (Po), L 11 Or L 14 are each independently a single bond or C 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of a11 to a14 are each independently selected from integers of 1 to 4; R 11 Or R 14 each independently represents a substituted or unsubstituted C 3 -C 30 Branched alkyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkyl groups, substituted or unsubstituted C 2 -C 30 Alkenyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkenyl groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkenyl groups, substituted or unsubstituted C 2 -C 30 Alkynyl groups, substituted or unsubstituted C 6 -C 30 Aryl groups, substituted or unsubstituted C 7 -C 30 Arylalkyl groups, substituted or unsubstituted C 1 -C 30 Heteroaryl groups, or substituted or unsubstituted C 2 -C30 is a heteroarylalkyl group, R 11 Or R 14 adjacent two of may be optionally bonded to each other to form a fused ring; b11 to b14 are each independently selected from integers of 1 to 4; Y 11 Or Y 13 are each independently O, O(C=O), S, S(C=O), NX14 or N(C=O); X 11 Or X 14 each independently represents a C which may optionally contain hydrogen, deuterium, or heteroatoms; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of Y 21 and Y 22 each independently represents a C having one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom; 1 -C 30 is a linear, branched or cyclic monovalent hydrocarbon radical of L 21 is a single bond, a double bond, or C 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of Each a21 is independently selected from an integer of 1 to 4; Y 21 , Y 22 and L 21 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0046] The molecular weight of the organometallic compound may be 3,000 g / mol or less. Specifically, the molecular weight of the organometallic compound may be 2,000 g / mol or less.

[0047] Without being limited to a particular theory, the organometallic compound may form radicals by heat and / or high energy radiation. 11 Radicals are formed from the carbon bonds, and optionally in an atmosphere in which water is present, the radicals react to form chemical bonds between the organometallic compounds, which can change the physical properties of the organometallic compounds, particularly their solubility in the developer.

[0048] The organometallic compounds represented by any one of the chemical formulas 1-1 to 1-4 are R 11 Or R 14 Since the organometallic compound represented by any one of formulas 1-1 to 1-4 contains at least one R 11 Or R 14 is not a linear alkyl group, but the radical formed by the hemolysis of the C-H bond is relatively unstable and the energy required for decomposition of the C-H bond is relatively high. 11 Or R 14 As such, linear alkyl groups are not suitable.

[0049] For example, in formulas 1-1 to 1-4, M 11 may be In, Sn or Sb. Specifically, in Chemical Formulas 1-1 to 1-4, M 11 may be Sn.

[0050] For example, in formulas 1-1 to 1-4, L 11 Or L 14 each independently represents a single bond, a substituted or unsubstituted C 1 -C 30 Alkyl groups, substituted or unsubstituted C 3 -C 30 Cycloalkylene groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkylene groups, substituted or unsubstituted C2 -C 30 Alkenylene group, substituted or unsubstituted C 3 -C 30 Cycloalkenylene group, substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene group, substituted or unsubstituted C 6 -C 30 An arylene group, or a substituted or unsubstituted C 1 -C 30 It may also be a heteroarylene group.

[0051] Specifically, in chemical formulas 1-1 to 1-4, L 11 Or L 14 are each independently a single bond; and deuterium, a halogen, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 1 -C 30 Alkylene group, C 3 -C 30 Cycloalkylene group, C 3 -C 30 Heterocycloalkylene group, C 2 -C 30 Alkenylene group, C 3 -C 30 Cycloalkenylene group, C 3 -C 30 Heterocycloalkenylene group, C 6 -C 30 Arylene Groups and C 1 -C 30 heteroarylene groups;

[0052] More specifically, in the formulas 1-1 to 1-4, L 11 Or L 14 each independently represents a single bond; and deuterium, halogen, a hydroxyl group, a cyano group, C 1 -C 20 Alkyl group, C 1 -C 20 C, substituted or unsubstituted with halogenated alkyl groups, or any combination thereof 1 -C 30 alkylene groups;

[0053] For example, in formulas 1-1 to 1-4, a11 to a14 may each independently be an integer of 1 or 2.

[0054] For example, in formulas 1-1 to 1-4, R 11 Or R 14each independently represents deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 3 -C 30 Branched alkyl group, C 3 -C 30 Cycloalkyl groups, C 3 -C 30 Heterocycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 3 -C30 Heterocycloalkenyl group, C 2 -C 30 Alkynyl group, C 6 -C 30 Aryl group, C 7 -C 30 Arylalkyl groups, C 1 -C 30 Heteroaryl groups and C 2 -C 30 heteroarylalkyl groups;

[0055] Specifically, in the chemical formulas 1-1 to 1-4, R 11 Or R 14 each independently represents deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 3 -C 30 Branched alkyl group, C 3 -C 30 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 2 -C 30 Alkynyl group, C 6 -C 30 Aryl groups and C 7 -C 30 arylalkyl groups;

[0056] More specifically, in formulas 1-1 to 1-4, R 11 Or R 14 may be independently selected from any one of the following formulas 3-1 to 3-15: [ka] Chemical formula 3-1 to 3-15: At least one hydrogen atom can be a deuterium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, or a C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 It may be optionally substituted with halogenated, alkylthio groups, or any combination thereof.

[0057] In the chemical formulas 1-1 to 1-4, b11 to b14 are each R 11Or R 14 For example, in Chemical Formulae 1-1 to 1-4, b11 to b14 may each independently be 1 or 2.

[0058] R 11 Or R 14 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0059] For example, multiple R 11 two adjacent R 12 two adjacent R 13 two adjacent R 14 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0060] Another example is R 11 Or R 14 Adjacent two of may optionally be bonded to each other to form a fused ring.

[0061] For example, in formulas 1-1 to 1-4, Y 11 Or Y 13 may each independently be O, O(C=O), S or S(C=O).

[0062] For example, in the chemical formulas 1-1 to 1-4, X 11 Or X 14 each independently represents hydrogen; deuterium; and deuterium, a halogen, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 1 -C 30 Alkoxy group, C 1 -C 30 Alkylthio group, C 1 -C 30 Halogenated alkoxy groups, C 1 -C 30 Halogenated alkylthio groups, C 3 -C 30 Cycloalkyl groups, C 3 -C 30 Cycloalkoxy group, C 3 -C 30 Cycloalkylthio group, C 3 -C 30 Heterocycloalkyl groups, C 2 -C 30Alkenyl 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 groups, C 1 -C 30 Heteroaryl groups, C 1 -C 30 Heteroaryloxy group, C 1 -C 30 Heteroarylthio groups and C 2 -C 30 heteroarylalkyl groups;

[0063] Specifically, in the chemical formulas 1-1 to 1-4, X 11 Or 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, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 3 -C 20 Cycloalkyl groups, C 6 -C 20 aryl groups, or any combination thereof, 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 3 -C 30 Cycloalkyl groups, C 2 -C30 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 groups, C 1 -C 30 Heteroaryl groups and C 2 -C 30 heteroarylalkyl groups;

[0064] More specifically, in the chemical formulas 1-1 to 1-4, X 11 Or X 14 are each independently hydrogen; deuterium; and C which is unsubstituted or substituted with deuterium, halogen, or any combination thereof. 1 -C 30 Alkyl group, C 3 -C 30 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 2 -C 30 Alkynyl groups and C 6 -C 30 aryl groups;

[0065] In particular, in the chemical formulas 1-1 to 1-4, X 11 Or X 14may each independently be selected from hydrogen; deuterium; and 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, unsubstituted or substituted with deuterium, a halogen, methyl, ethyl, phenyl, naphthyl, or any combination thereof.

[0066] In one embodiment, the organometallic compound represented by any one of Formulas 1-1 to 1-4 may be selected from Group I: [ka] [ka] In Group I, n is an integer from 1 to 4.

[0067] For example, in Group I, n may be 2.

[0068] For example, in formula 2, Y 21 is represented by any one of the following chemical formulas 4-1 to 4-5, 22 may be represented by any one of the following chemical formulas 4-6 to 4-10: [ka] Chemical formula 4-1 to 4-10: X 41 and X 44 are each independently 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 41and Y 42 are each independently C, S or P; A 41 X 43 C containing as a ring member 1 -C 30 is a heterocyclic group, A 42 X 46 C containing as a ring member 1 -C 30 is a heterocyclic group, R 41 Or R 44 are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid group, or C 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of b41 and b42 are each independently selected from integers of 1 to 10; * indicates a bonding site with an adjacent atom.

[0069] In one embodiment, the additive is X 41 Or X 43 One of the following is selected: 44 Or X 46 and any metal atom, for example, M 11 may include a structure in which the ring is coordinated to form a 5-, 6-, or 7-membered ring.

[0070] For example, in formulas 4-5 and 4-10, 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 and one or more second rings are fused to each other, the first ring is tetrahydropyrane, dihydropyrane, pyran, tetrahydrothiopyrane, dihydrothiopyrane, thiopyrane, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine, or triazine; The second ring may be cyclopentane, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene, or naphthalene. Specifically, in chemical formulas 4-5 and 4-10, 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 and one or more second rings are fused to each other, the first ring is tetrahydropyran, dihydropyran, pyran, tetrahydrothiopyran, dihydrothiolane, thiopyran, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine, or triazine; The second ring may be benzene.

[0071] For example, in formulas 4-1 to 4-10, R 41 Or R 44each independently represents hydrogen; deuterium; a halogen; a cyano group; a nitro group; a hydroxyl group; a thiol group; an amino group; a carboxylic acid group; and deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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 acid anhydride moiety, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 3 -C 30 Cycloalkyl groups, C 3 -C 30 Heterocycloalkyl groups, 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 groups, C 1 -C 30 Heteroaryl groups and C 2 -C 30 heteroarylalkyl groups;

[0072] Specifically, in the chemical formulas 4-1 to 4-10, R 41 Or R 44 each independently represents hydrogen; deuterium; a halogen; a cyano group; a nitro group; a hydroxyl group; a thiol group; an amino group; a carboxylic acid group; and deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 3 -C 20 Cycloalkyl groups, C 6 -C 20 aryl groups, or any combination thereof, 1 -C 30 Alkyl group, C 1 -C 30 Halogenated alkyl groups, C 3 -C 30 Cycloalkyl groups, C 2 -C 30 Alkenyl group, C 3 -C 30 Cycloalkenyl group, C 3 -C 30 Heterocycloalkenyl group, C2 -C 30 Alkynyl group, C 6 -C 30 Aryl group, C 7 -C 30 Arylalkyl groups, C 1 -C 30 Heteroaryl groups and C 2 -C 30 heteroarylalkyl groups;

[0073] In one embodiment, in Formula 2, i) Y 21 is represented by the chemical formula 4-5, and Y 22 is represented by any one of chemical formulas 4-6 to 4-10, or ii) Y 21 is represented by any one of chemical formulas 4-1 to 4-5, and Y 22 can be represented by formula 4-10.

[0074] In another embodiment, in Formula 2, Y 21 is represented by the chemical formula 4-5, and Y 22 can be represented by formula 4-10.

[0075] For example, in formula 2, L 21 is a single bond, double bond, substituted or unsubstituted C 1 -C 30 Alkylene group, substituted or unsubstituted C 3 -C 30 Cycloalkylene groups, substituted or unsubstituted C 3 -C 30 Heterocycloalkylene groups, substituted or unsubstituted C 2 -C 30 Alkenylene group, substituted or unsubstituted C 3 -C 30 Cycloalkenylene group, substituted or unsubstituted C 3 -C 30 Heterocycloalkenylene group, substituted or unsubstituted C 6 -C 30 An arylene group, or a substituted or unsubstituted C 1 -C 30It may also be a heteroarylene group.

[0076] Specifically, in formula 2, L 21 is a single bond; a double bond; and deuterium, a halogen, a cyano group, a nitro group, a hydroxy group, a thiol group, an amino group, a carboxylic acid 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, C 1 -C 20 Alkyl group, C 1 -C 20 Halogenated alkyl groups, C 1 -C 20 Alkoxy group, C 1 -C 20 Alkylthio group, C 1 -C 20 Halogenated alkoxy groups, C 1 -C 20 Halogenated alkylthio groups, C 3 -C 20 Cycloalkyl groups, C 3 -C 20 Cycloalkoxy group, C 3 -C 20 Cycloalkylthio group, C 6 -C 20 Aryl group, C 1 -C 20 Heteroaryl groups, C 6 -C 20 Aryloxy group, C 6 -C 20 Arylthio group, C 1 -C 20 Heteroaryloxy group, C 1 -C 20 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 1 -C 30 Alkylene group, C 3 -C 30 Cycloalkylene group, C 3 -C 30 Heterocycloalkylene group, C 2-C 30 Alkenylene group, C 3 -C 30 Cycloalkenylene group, C 3 -C 30 Heterocycloalkenylene group, C 6 -C 30 Arylene Groups and C 1 -C 30 heteroarylene groups;

[0077] More specifically, in formula 2, L 21 is a single bond; a double bond; and deuterium, halogen, hydroxyl group, cyano group, C 1 -C 20 Alkyl group, C 1 -C 20 C, substituted or unsubstituted with halogenated alkyl groups, or any combination thereof 1 -C 30 Alkylene group and C 2 -C 30 alkenylene groups;

[0078] In one embodiment, the additive may be represented by the following formula 2-1: [ka] In chemical formula 2-1, X 43 , X 46 , A 41 , A 42 , L 21 , a21, R 41 Or R 44 For explanations of b41, b42, please refer to the above.

[0079] In one embodiment, the additive may be represented by the following formula 2-11 or 2-12: [ka] In chemical formulas 2-11 and 2-12, X 43 and X 46are each independently O, S, N or P; A 41 X 43 C containing as a ring member 1 -C 30 is a heterocyclic group, A 42 X 46 C containing as a ring member 1 -C 30 is a heterocyclic group, Z 21 and Z 22 are each independently C or N; Z 21 and Z 22 The bond to is a single bond or a double bond, L 22 is a single bond; a double bond; and deuterium, halogen, hydroxyl group, cyano group, C 1 -C 20 Alkyl group, C 1 -C 20 C, substituted or unsubstituted with halogenated alkyl groups, or any combination thereof 1 -C 30 Alkylene group and C 2 -C 30 alkenylene groups; a22 is selected from the group consisting of integers from 1 to 4; R 41 Or R 44 are each independently 1 -C 30 is a linear, branched or cyclic divalent hydrocarbon radical of b41 and b42 are each independently selected from integers of 1 to 10.

[0080] In formulas 2-11 and 2-12, X 43 and Z 21 Bonds with and Z 22 and X 46 Each bond to may independently be a single bond or a double bond.

[0081] For example, in formulas 2-11 and 2-12, X 43and X 46 There can be three chemical bonds between X 43 and Z 21 Chemical bond with Z 21 and Z 22 Chemical bonds with and Z 22 and X 46 This includes chemical bonding with

[0082] In one embodiment, the additive may be selected from Group II: [ka]

[0083] The additive contains N, O, S and / or P that provide an unshared electron pair and can therefore provide a coordinate bond to the organometallic compound, thereby improving the chemical stability of the organometallic compound.

[0084] The organometallic compound may be any one of those represented by any one of Chemical Formulas 1-1 to 1-4, or two or more of them may be mixed and used. Similarly, the additive may be any one of the compounds represented by Chemical Formula 2, or two or more of them may be mixed and used.

[0085] In the resist composition, the organometallic compound is present in an amount of 0.01 to 100 parts by weight, specifically, 0.2 or more parts by weight, 0.5 or more parts by weight, 1 or more parts by weight, or 1.5 or more parts by weight, or may be 90 or less parts by weight, or 80 or less parts by weight, relative to 100 parts by weight of the resist composition. If the above-mentioned range is satisfied, chemical bonds between the organometallic compounds are sufficiently formed, while side reactions are suppressed, making it possible to provide a resist composition with improved sensitivity and / or resolution.

[0086] In the resist composition, the additive is added in an amount of 0.01 to 100 parts by weight, specifically, 0.2 or more parts by weight, 0.5 or more parts by weight, 1 or more parts by weight, or 1.5 or more parts by weight, or may be added in an amount of 90 or less parts by weight, or 80 or less parts by weight, relative to 100 parts by weight of the resist composition. If the above-mentioned range is satisfied, chemical bonds between the organometallic compounds are sufficiently formed while side reactions are suppressed, making it possible to provide a resist composition with improved sensitivity and / or resolution.

[0087] In the resist composition, the additive may be contained in an amount of 0.1 to 100,000 parts by weight based on 100 parts by weight of the organometallic compound. Specifically, the additive may be contained in an amount of 10 to 1,000 parts by weight based on 100 parts by weight of the organometallic compound. If the above range is satisfied, the photosensitivity of the resist composition can be maintained at the same level as that of a resist composition not containing the additive, while the storage stability can be significantly improved.

[0088] The resist composition changes in solubility in a developer by exposure to high-energy radiation. The resist composition may be a negative resist composition in which a non-exposed portion of a resist film is dissolved and removed to form a negative resist pattern, or a positive resist composition in which an exposed portion of a resist film is dissolved and removed to form a positive resist pattern. The resist composition can be modified in various ways, for example, it may be either a negative type or a positive type, depending on the exposure intensity and / or the type of developer.

[0089] Furthermore, the resist composition according to one embodiment may be for an alkaline development process in which an alkaline developer is used for the development treatment when forming a resist pattern, or may be for a solvent development process in which a developer containing an organic solvent (hereinafter also referred to as an "organic developer") is used for the development treatment.

[0090] The resist composition is of a non-chemically amplified type and therefore does not substantially contain a photoacid generator.

[0091] The resist composition contains substantially no compounds with a molecular weight of 1,000 or more other than the organometallic compound, because the physical properties of the organometallic compound change upon exposure to light. The organometallic compounds and additives may be prepared by any suitable method or may be obtained commercially.

[0092] The structure (composition) of the organometallic compound can be confirmed by carrying out Fourier transform infrared (FT-IR) analysis, nuclear magnetic resonance (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) analysis, size exclusion chromatography (SEC) analysis, thermal analysis, etc. Detailed confirmation methods are as described in the Examples.

[0093] <Organic solvent> The resist composition may further contain an organic solvent.

[0094] 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 contained as necessary. One type of organic solvent may be used, or two or more different types may be used in combination.

[0095] In one embodiment, the organic solvent may include a protic organic solvent, an aprotic organic solvent, or any combination thereof. In other embodiments, the organic solvent may be a mixture of aprotic and protic organic solvents.

[0096] Since the resist composition is substantially free of water, the organic solvent is free of water. Specifically, the resist composition may contain 3% by weight or less of water, and the organic solvent may contain 3% by weight or less of water.

[0097] Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, sulfoxide-based solvents, and hydrocarbon-based solvents.

[0098] More specifically, examples of alcohol-based solvents include 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, Monoalcohol solvents such as n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, and diacetone alcohol; polyhydric alcohol 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, and tripropylene glycol;Examples of the polyhydric alcohol-containing ether solvents include 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, and dipropylene glycol monopropyl ether.

[0099] Examples of the ether solvent 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.

[0100] 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; 2,4-pentanedione, acetonylacetone, and acetophenone.

[0101] 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.

[0102] Examples of ester-based solvents include 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, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, Acetate ester solvents such as acetate, methylcyclohexyl acetate, n-nonyl acetate; 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 Examples of the solvent include polyhydric alcohol-containing ether carboxylate solvents such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monoethyl ether acetate; lactone solvents such as γ-butyrolactone and δ-valerolactone; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate; lactate ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate; 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, and diethyl phthalate.

[0103] Examples of the sulfoxide solvent include dimethyl sulfoxide and diethyl sulfoxide.

[0104] Examples of the hydrocarbon solvent 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; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-amylnaphthalene.

[0105] Specifically, the organic solvent may be selected from alcohol-based solvents, ketone-based solvents, ester-based solvents, and any combination thereof. More specifically, the 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 any combination thereof.

[0106] The organic solvent may be included in an amount of 0 to 99.9 parts by weight per 100 parts by weight of the resist composition. One type of organic solvent may be used, or two or more different types may be mixed and used.

[0107] <Optional ingredients> If necessary, the resist composition may further contain a surfactant, a crosslinking agent, a leveling agent, a colorant, or any combination thereof.

[0108] The resist composition may further contain a surfactant in order to improve the coating property, the developability, etc. Specific examples of the surfactant include nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. As the surfactant, a commercially available product or a synthetic product can be used. Examples of commercially available surfactants include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, Polyflow No. 95 (all manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP EF301, EFTOP EF303, EFTOP EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE (registered trademark) F171, MEGAFACE F173, R40, R41, R43 (all manufactured by DIC Corporation), Fluorad (registered trademark) FC430, Fluorad FC431 (all manufactured by 3M), AsahiGuard AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (all manufactured by AGC Seimi Chemical Co., Ltd.).

[0109] The surfactant may be contained in an amount of 0 to 20 parts by weight per 100 parts by weight of the resist composition. One type of surfactant may be used, or two or more different types may be mixed and used.

[0110] The method for producing the resist composition is not particularly limited, and for example, a method of mixing the 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.

[0111] [Pattern formation method] The pattern forming method according to the exemplary embodiment will be described in more detail below with reference to Figures 1, 2A, and 2A to 2C. Figure 1 is a flow chart showing the pattern forming method according to the exemplary embodiment, and Figures 2A to 2C are side cross-sectional views showing the pattern forming method according to the exemplary embodiment. The pattern forming method using a negative resist composition will be described below as an example, but is not limited thereto.

[0112] 1, the method for forming a pattern includes a step of applying a resist composition to form a resist film (S101), a step of exposing at least a part of the resist film to high energy radiation (S102), and a step of developing the exposed resist film using a developer (S103). The steps may be omitted or performed in a different order as necessary.

[0113] First, a substrate 100 is provided. The substrate 100 may be a semiconductor substrate such as a silicon substrate or a germanium substrate, glass, quartz, ceramic, copper, etc. In some embodiments, the substrate 100 may include a III-V compound such as GaP, GaAs, or GaSb.

[0114] A resist composition can be applied to a substrate 100 to a desired thickness, specifically by a coating method, to form a resist film 110. If necessary, the resist film 110 can be heated (pre-baked (PB)) to remove any organic solvent remaining therein. Alternatively, the resist film 110 can be heated to generate radicals, and then exposed to light to chemically bond the radicals to form crosslinks.

[0115] The coating method may be spin coating, dipping, roller coating, or other common coating methods. Among them, spin coating may be used in particular, and the resist film 110 may have a desired thickness by adjusting the viscosity, concentration, and / or spin speed of the resist composition. Specifically, the thickness of the resist film 110 may be 10 nm to 300 nm. More specifically, the thickness of the resist film 110 may be 30 nm to 200 nm.

[0116] The lower limit of the pre-bake temperature may be 60° C. or more, specifically, 80° C. or more. The upper limit of the pre-bake temperature may be 150° C. or less, specifically, 140° C. or less. The lower limit of the pre-bake time may be 5 seconds or more, specifically, 10 seconds or more. The upper limit of the pre-bake time may be 600 seconds or less, specifically, 300 seconds or less. Before applying the resist composition to the substrate 100, a layer to be etched (not shown) may be further formed on the substrate 100. The layer to be etched may refer to a layer to which an image is transferred from a resist pattern and converted into a predetermined pattern. In one embodiment, the layer to be etched may be formed to include an insulating material such as silicon oxide, silicon nitride, or silicon oxynitride. In some embodiments, the layer to be etched may be formed to include a conductive material such as a metal, a metal nitride, a metal silicide, or a metal silicide nitride film. In some embodiments, the layer to be etched may be formed to include a semiconductor material such as polysilicon.

[0117] In one embodiment, in order to maximize the efficiency of the resist, an anti-reflective coating may be further formed on the substrate 100. The anti-reflective coating may be an organic or inorganic anti-reflective coating.

[0118] 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. Furthermore, when performing immersion exposure, in order to prevent direct contact between the immersion medium and the resist film 100, for example, a protective film for immersion can be provided on the resist film 100.

[0119] Next, at least a portion of the resist film 110 may be exposed to high-energy radiation. For example, at least a portion of the resist film 110 may be irradiated with high-energy radiation that has passed through a mask 120. As a result, the resist film 110 may have an exposed portion 111 and a non-exposed portion 112.

[0120] Without being limited to a particular theory, it is believed that exposure to light generates radicals in the exposed areas 111, and chemical bonds are formed between the radicals, which may change the physical properties of the resist composition.

[0121] This exposure is sometimes performed by irradiating a high-energy beam through a mask having a predetermined pattern using a liquid medium such as water. Examples of high-energy beams include electromagnetic waves such as ultraviolet, far ultraviolet, extreme ultraviolet (EUV (extreme ultraviolet); wavelength 13.5 nm), X-rays, and gamma rays; and charged particle beams such as electron beams (EB) and alpha rays. Irradiation with such high-energy beams can be collectively called "exposure".

[0122] The exposure light source is a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), or a F 2 A variety of lasers can be used, such as those that emit laser light in the ultraviolet region, such as an excimer laser (wavelength 157 nm), those that convert the wavelength of laser light from a solid-state laser light source (such as a YAG laser or semiconductor laser) to emit harmonic laser light in the far ultraviolet region or vacuum ultraviolet region, and those that irradiate electron beams or extreme ultraviolet (EUV). During exposure, exposure is generally performed through a mask that corresponds to the desired pattern, but if the exposure light source is an electron beam, exposure can also be performed by direct writing without using a mask.

[0123] For example, when extreme ultraviolet rays are used as high-energy rays, the cumulative dose is 2,000 mJ / cm 2 Specifically, 500 mJ / cm 2 In addition, when an electron beam is used as the high energy beam, the cumulative dose is 5,000 μC / cm 2 Specifically, 1,000μC / cm 2 It may be the following.

[0124] After the exposure, a post-exposure bake (PEB) may be performed. The lower limit of the PEB temperature may be 50° C. or more, specifically 80° C. or more. The upper limit of the PEB temperature may be 250° C. or less, specifically 200° C. or less. The lower limit of the PEB time may be 5 seconds or more, specifically 10 seconds or more. The upper limit of the PEB time may be 600 seconds or less, specifically 300 seconds or less.

[0125] Next, a developer may be used to develop the exposed resist film 110. The non-exposed portions 112 are washed away by the developer and removed, while the exposed portions 111 are not washed away by the developer and remain.

[0126] 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 development method include a dipping method, a paddle method, a spray method, a dynamic administration method, etc. The development temperature may be, for example, 5° C. or more and 60° C. or less, and the development time may be, for example, 5 seconds or more and 300 seconds or less.

[0127] 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.

[0128] The lower limit of the alkaline compound content in the alkaline developer may be 0.1% by weight or more, specifically 0.5% by weight or more, more specifically 1% by weight or more, and the upper limit of the alkaline compound content in the alkaline developer may be 20% by weight or less, specifically 10% by weight or less, more specifically 5% by weight or less.

[0129] The organic solvent contained in the organic developer may be, for example, the same organic solvent as exemplified in the <Organic solvent> section of [Resist composition]. Specifically, nBA (n-butyl acetate), PGME (propylene glycol methyl ether), PGMEA (propylene glycol methyl ether acetate), GBL (γ-butyrolactone), IPA (isopropanol), etc. may be used as the organic developer. The organic developer may further contain an organic acid such as acetic acid, formic acid, or citric acid.

[0130] The lower limit of the organic solvent content in the organic developer may be 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. The organic developer also contains a surfactant. The organic developer also contains a small amount of water. During development, the organic developer can be replaced with a different type of solvent to stop the development.

[0131] The resist pattern after development may be further washed. As the washing liquid, ultrapure water, a rinse liquid, etc. may be used. As the rinse liquid, there is no particular limitation as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent may be used. For example, the rinse liquid may be an alcohol-based solvent or an ester-based solvent. After washing, the rinse liquid remaining on the substrate and the pattern may be removed. In addition, when ultrapure water is used, the water remaining on the substrate and the pattern may be removed.

[0132] The developer may be used alone or in combination of two or more kinds. As described above, after forming a resist pattern, a patterned wiring board can be obtained by etching. The etching method can be a known method such as dry etching using plasma gas, and wet etching using an alkaline solution, a cupric chloride solution, a ferric chloride solution, etc.

[0133] After the resist pattern is formed, plating can be carried out. The plating method is not particularly limited, but examples thereof include copper plating, solder plating, nickel plating, and gold plating.

[0134] The remaining resist pattern after etching can be peeled off by an organic solvent. Examples of such organic solvents are not particularly limited, but include, for example, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate). The peeling method is not particularly limited, but includes, for example, a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board and may have a small diameter through hole.

[0135] In one embodiment, the wiring board can be formed by a method in which a resist pattern is formed, a metal is evaporated in a vacuum, and then the resist pattern is dissolved in a solution, that is, a lift-off method.

[0136] 4A-4E are cross-sectional side views illustrating a method of forming a patterning structure according to one embodiment of the present invention.

[0137] As shown in FIG. 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 top of the material layer 130. The material layer 130 may include an insulating material (e.g., silicon oxide, silicon nitride), a semiconductor material (e.g., silicon), or a metal (e.g., copper). In some embodiments, the material layer 130 may have a multi-layer structure. The material of the material layer 130 may be different from the material of the substrate 100.

[0138] As shown in FIG. 4B, the resist film 110 may undergo a pre-exposure bake process and then be exposed to high-energy light through a mask 120, after which the resist film 110 may include an exposed portion 111 and an unexposed portion 112.

[0139] 4C, the exposed resist film 110 can be developed using a developer, where the non-exposed portions 112 are washed away by the developer, and the exposed portions 111 remain unwashed by the developer.

[0140] As shown in FIG. 4D, the exposed portions 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. As shown in FIG. 4E, the resist pattern 110 may be removed.

[0141] 5A-5E are cross-sectional side views illustrating a method of forming a semiconductor device according to one embodiment of the present invention.

[0142] 5A, a gate dielectric 505 (e.g., silicon oxide) may be formed on a substrate 500. The substrate 500 may be a semiconductor substrate, such as a silicon substrate. A gate layer 515 (e.g., doped polysilicon) may be formed on the gate dielectric 505. A hard mask layer 520 may be formed on the gate layer 515.

[0143] 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 an embodiment of the present invention. The resist composition may include an organic solvent.

[0144] As shown in FIG. 5C, the gate layer 515 and the gate dielectric 505 may be etched to form a hard mask pattern 520a, a gate electrode pattern 515a, and a gate dielectric pattern 505a.

[0145] As shown in FIG. 5D, 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., chemical vapor deposition (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 the spacers 535a are formed, ions may be implanted into the substrate 500 to form source / drain impurity regions (S / D).

[0146] 5E, an interlayer insulating film 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 film 560 to be connected to the gate electrode 515a and the source / drain impurity regions (S / D) regions. The electrical contacts 570a, 570b, and 570c may be formed of a conductive material (e.g., metal). Although not shown, a barrier layer may be formed between the sidewalls of the interlayer insulating film 560 and the electrical contacts 570a, 570b, and 570c.

[0147] Although Figures 5A-5E illustrate an example of forming a transistor, the invention is not so limited.

[0148] The resist composition according to one or more embodiments may be used in patterning processes to form other types of semiconductor devices. The resist composition may include an organic solvent.

[0149] 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 to the following examples. EXAMPLES

[0150] Synthesis Example 1: Synthesis of SM1 [ka]

[0151] 8.2g (69.2mmol) of tin powder and 120ml of dry toluene were placed in a 250ml three-neck flask, and the temperature was raised to 90°C. After adding 1.0ml of deionized water, 10.0g (69.2mmol) of 4-fluorobenzyl chloride was added dropwise for 10 minutes. After heating and refluxing at 130°C for 4 hours and stirring, the unreacted tin powder was filtered out using a Buchner funnel. At the same time, the filtered solution was cooled, and 6.5g (yield 36%) of the product, white crystals (SM1 precursor), was obtained.

[0152] [ka]

[0153] 1.5g (3.7mmol) of SM1 precursor and 21.0ml of dry acetone were placed in a 50ml single-neck flask and cooled to 0°C. 0.6g (7.4mmol) of sodium acetate was added and stirred for 12 hours. The NaCl salt generated in the solution was filtered using a 0.45μm filter, concentrated by rotary evaporation, and dried in vacuum to obtain SM1 (1.6g) with a yield of 74%. 1 H-NMR (500 MHz, DMSO-d 6 ): δ ~6.9 (8H), ~2.6 (4H), ~1.6 (6H)

[0154] Production example: Production of casting solution The organometallic compound synthesized in Synthesis Example 1 was dissolved in ethyl lactate at 2 wt %, and 0.5 equivalents (based on 1 equivalent of the organometallic compound) of the additives shown in Table 1 below were further added thereto to obtain casting solutions A-1 to A-4.

[0155] Casting solutions A-1 to A-4 were stored in a 40° C. oven for 12 days, and then casting solutions B-1 to B-4 were obtained.

[0156] [Table 1] In Table 1, post-treatment means storage in a 40° C. oven for 12 days.

[0157] Evaluation example 1: Storage stability evaluation (1) Visual evaluation The changes over time of casting solutions B-1 to B-4 were judged with the naked eye. There was no change over time for casting solutions B-2 to B-4, which contained additives, but there was a change visible to the naked eye for casting solution B-1, which did not contain additives.

[0158] (2) Surface roughness (Rq) evaluation An 8-inch diameter silicon wafer was cut into quarters and then heated in O for 30 min. 2 After the plasma treatment, casting solutions A-1 to A-4 and casting solutions B-1 to B-4 were spin-coated at 1,500 rpm for 1 minute, and then dried (PAB) at 120°C for 1 minute to prepare films having the initial thicknesses shown in Table 2 below. Then, a 3.5 mm thick zig (4x4) with rectangular holes (1cmx1cm) was placed on the films obtained using casting solutions B-1 to B-4, and deep ultraviolet (DUV) with a wavelength of 254 nm was applied to each hole at 0 to 100 mJ / cm. 2 and dried (PEB) at 200° C. for 1 minute. The dried film was immersed in a PGMEA solution in which 2 wt % acetic acid was dissolved as a developer at 25° C. for 60 seconds, and the surface of the remaining film was observed using an atomic force microscope, and Rq was calculated from the average height observed. The results are shown in Table 2 below.

[0159] [Table 2]

[0160] Referring to Table 2, in the case of Comparative Example 2-1 in which no additive was added, the thickness of the thin film formed after high temperature storage was significantly thinner than before storage, indicating that the storage stability was low. However, in the cases of Examples 2-1 to 2-3 in which additives were added, the thickness of the thin film was maintained at a similar level to before storage even after high temperature storage, indicating that the storage stability was relatively high.

[0161] In addition, in the case of Examples 2-1 to 2-3 containing the additive, Rq was lower than that of Comparative Example 2-1, which indicates that the coating characteristics of the resist composition containing the additive are improved.

[0162] Evaluation example 2: Thin film development evaluation The SM1 obtained in Synthesis Example 1 was dissolved in ethyl lactate at 2% by weight, and 0.2 equivalents of compound A was further added thereto as an additive (SM1: compound A = 12: 1 (mass ratio)) to obtain casting solution C-1. Also, casting solution C-2, which had the same composition as casting solution C-1 except that compound A was not added, was obtained. A silicon wafer having a diameter of 4 inches was placed on O 2 After the plasma treatment, casting solutions C-1 and C-2 were spin-coated at 1,200 rpm for 1 minute, and then dried (PAB) at 90°C for 1 minute to produce films with the initial thicknesses shown in Table 3 below. Then, a 3.5 mm thick zig (4x4) with rectangular holes (1cmx1cm) was placed on top of the films, and DUV with a wavelength of 254 nm was applied to each hole at 0 to 100 mJ / cm. 2 The film was exposed to a dose of 100 nm and dried at 200° C. for 1 minute (PEB). The dried film was immersed in a PGMEA solution containing 2% by weight of acetic acid as a developer at 25° C. for 60 seconds, and the remaining film thickness was measured and shown in Table 3 below and in FIGS. 3A and 3B. In FIGS. 3A and 3B, “as-coated” refers to the reference data for the sample after PAB, “after PEB” refers to the reference data for the sample after PEB and before treatment with the developer, and “after develop” refers to the data for the sample treated with the developer.

[0163] [Table 3]

[0164] In Table 3, E th means the exposure dose at which the thin film begins to harden, and E 1 means the exposure dose at which the film thickness saturates and does not increase any more.

[0165] Referring to Table 3, E in Example 3-1 th and E 1 is E of Comparative Example 3-1 th and E 1 It can be confirmed that the photosensitivity is not decreased by the use of the additive. [Explanation of symbols]

[0166] 100, 500 boards 110 Resist film 111 Exposure section 112 Non-exposed area 120 Mask 130 Material layer 135 Material Patterns 505 Gate Dielectric 505a Gate dielectric pattern 515 Gate Layer 515a Gate electrode pattern 520 Hard Mask Layer 520a hard mask pattern 535a Spacer 540b Resist pattern 560 Interlayer insulating film 570a, 570b, 570c Electrical contacts

Claims

1. An organometallic compound represented by any one of the following chemical formulas 1-1 to 1-4, A resist composition comprising an additive represented by the following chemical formula 2: 【Chemistry 1】 In the 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 Or L １４ are each independently a single bond, or C １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of a11 to a14 are each independently selected from integers of 1 to 4; R １１ Or R １４ each independently represents a substituted or unsubstituted C ３ -C ３０ Branched alkyl groups, substituted or unsubstituted C ３ -C ３０ Cycloalkyl groups, substituted or unsubstituted C ３ -C ３０ Heterocycloalkyl groups, substituted or unsubstituted C ２ -C ３０ Alkenyl group, substituted or unsubstituted C ３ -C ３０ Cycloalkenyl group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenyl group, substituted or unsubstituted C ２ -C ３０ Alkynyl group, substituted or unsubstituted C ６ -C ３０ Aryl group, substituted or unsubstituted C ７ -C ３０ Arylalkyl groups, substituted or unsubstituted C １ -C ３０ Heteroaryl group, or substituted or unsubstituted C ２ -C ３０ is a heteroarylalkyl group, R １１ Or R １４ adjacent two of may be optionally bonded to each other to form a fused ring; b11 to b14 are each independently selected from integers of 1 to 4; Y １１ Or Y １３ are each independently O, O(C=O), S, S(C=O), NX14 or N(C=O); X １１ Or X １４ each independently represents hydrogen, deuterium, or C, which may optionally contain heteroatoms; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of Y ２１ and Y ２２ each independently represents a C group containing one or more heteroatoms selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom; １ -C ３０ is a linear, branched or cyclic monovalent hydrocarbon radical of L ２１ is a single bond, a double bond, or C １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of Each a21 is independently selected from an integer of 1 to 4; Y ２１ , Y ２２ and L ２１ Adjacent two of may optionally be bonded to each other to form a fused ring.

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

3. L １１ Or L １４ each independently represents a single bond, a substituted or unsubstituted C １ -C ３０ Alkylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group, substituted or unsubstituted C ２ -C ３０ Alkenylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group, substituted or unsubstituted C ６ -C ３０ an arylene group, or a substituted or unsubstituted C １ -C ３０ 2. The resist composition according to claim 1, wherein the group is a heteroarylene group.

4. R １１ Or R １４ each independently represents deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid 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 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 groups, 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 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; ３ -C ３０ Branched 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 groups and C ２ -C ３０ 2. The resist composition according to claim 1, wherein the aryl group is selected from the group consisting of a heteroaryl alkyl group and a heteroaryl alkyl group.

5. Y １１ Or Y １３ The resist composition according to claim 1 , wherein each independently is O, O(C═O), S or S(C═O).

6. X １１ Or 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 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 groups, 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 C, substituted or unsubstituted with heteroarylthio groups, or any combination thereof; 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 groups, 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 groups and C ２ -C ３０ 2. The resist composition according to claim 1, wherein the aryl group is selected from the group consisting of a heteroaryl alkyl group and a heteroaryl alkyl group.

7. The resist composition according to claim 1, wherein the organometallic compound represented by any one of Chemical Formulas 1-1 to 1-4 is selected from the following Group I: 【Chemistry 2-1】 【Chemistry 2-2】 In Group I, n is an integer from 1 to 4.

8. Y ２１ is represented by any one of the following chemical formulas 4-1 to 4-5: Y ２２ is represented by any one of the following chemical formulas 4-6 to 4-10: 【Chemistry 3】 In the above Chemical Formulas 4-1 to 4-10, X ４１ and X ４４ are each independently 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 ４１ and Y ４２ are each independently C, S or P; A ４１ , X ４３ C containing as a ring member １ -C ３０ is a heterocyclic group, A ４２ , X ４６ C containing as a ring member １ -C ３０ is a heterocyclic group, R ４１ Or R ４４ are each independently hydrogen, deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a thiol group, an amino group, a carboxylic acid group, or C １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of b41 and b42 are each independently selected from an integer of 1 to 10; * indicates a bonding site with an adjacent atom.

9. 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 and one or more second rings are fused to each other, the first ring is tetrahydropyran, dihydropyran, pyran, tetrahydrothiopyran, dihydrothiolane, thiopyran, tetrahydrofuran, dihydrofuran, tetrahydrothiophene, dihydrothiophene, piperidine, tetrahydropyridine, dihydropyridine, pyrrolidine, dihydropyrole, pyrrole, imidazole, pyrazole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyridazine, pyrimidine, or triazine; 9. The resist composition according to claim 8, wherein the second ring is cyclopentane, cyclopentadiene, cyclohexane, cyclohexene, cyclohexadiene, benzene or naphthalene.

10. Y ２１ is represented by the above chemical formula 4-5, and Y ２２ is represented by any one of the formulas 4-6 to 4-10; or Y ２１ is represented by any one of formulas 4-1 to 4-5; Y ２２ The resist composition according to claim 8, wherein the compound is represented by any one of Chemical Formulas 4 to 10.

11. L ２１ is a single bond, a double bond, a substituted or unsubstituted C １ -C ３０ Alkylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkylene group, substituted or unsubstituted C ２ -C ３０ Alkenylene group, substituted or unsubstituted C ３ -C ３０ Cycloalkenylene group, substituted or unsubstituted C ３ -C ３０ Heterocycloalkenylene group, substituted or unsubstituted C ６ -C ３０ an arylene group, or a substituted or unsubstituted C １ -C ３０ 2. The resist composition according to claim 1, wherein the group is a heteroarylene group.

12. The resist composition according to claim 1, wherein the additive is represented by the following chemical formula 2-1: 【Chemistry 4】 In the above Chemical Formula 2-1, X ４３ and X ４６ are each independently O, S, N or P; A ４１ , X ４３ C containing as a ring member １ -C ３０ is a heterocyclic group, A ４２ , X ４６ C containing as a ring member １ -C ３０ is a heterocyclic group, L ２１ is a single bond, a double bond, or C １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of Each a21 independently represents an integer of 1 to 4; R ４１ Or R ４４ are each independently １ -C ３０ is a linear, branched or cyclic divalent hydrocarbon radical of b41 and b42 are each independently selected from an integer of 1 to 10; R ４１ , R ４３ and L ２１ Adjacent two of may optionally be bonded to each other to form a fused ring.

13. 2. The resist composition according to claim 1, wherein the additive is selected from the following Group II: 【Chemistry 5】

14. 2. 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.

15. The resist composition of claim 1 which is substantially free of a photoacid generator.

16. 2. The resist composition according to claim 1, which is substantially free of compounds having a molecular weight of 1,000 or more.

17. A step of applying a resist composition according to any one of claims 1 to 16 to form a resist film; exposing at least a portion of the resist film to high energy radiation; and developing the exposed resist film using a developer.

18. 20. The method of claim 17, wherein the exposing step is performed by irradiating with deep ultraviolet (DUV), extreme ultraviolet (EUV) and / or electron beam (EB).

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

20. the exposed resist film includes an exposed portion and a non-exposed portion, The pattern formation method according to claim 17 , wherein the unexposed portion is removed in the developing step.

Images