Compound or cluster compound, method for producing compound, photosensitive composition containing compound, pattern forming method using composition, substrate, and method for manufacturing substrate

Abstract

Provided is a compound capable of obtaining a highly practical photosensitive composition that can be used as a photoresist to form ultra-fine patterns.　A compound according to the present invention contains a metal atom and a carboxylate ligand A having a cyclic structure. The carboxylate ligand A has a cyclic structure bonded to a carboxylate group. In the cyclic structure, carbon C1 in the cyclic structure bonded to the carboxylate group is tertiary or quaternary carbon. Carbon C2 adjacent to carbon C1 in the cyclic structure has a substituent R1. The substituent R1 is an organic group or a halogen atom.

Description

Compound or cluster compound, method for producing the compound, photosensitive composition containing the compound, pattern forming method using the composition, substrate and method for producing the substrate

[0001] The present invention relates to a compound or cluster compound that is suitable for use in ultra-microlithography processes such as the production of ultra-LSIs and high-capacity microchips, and other photofabrication processes, a method for producing the compound, a photosensitive composition containing the compound, a pattern formation method using the photosensitive composition, a substrate, and a method for producing the substrate.

[0002] In the semiconductor device manufacturing process, microfabrication is performed using lithography with photoresist compositions. In semiconductor photolithography, circuit patterns become smaller as semiconductor devices become smaller, according to Moore's Law, and further miniaturization is desired. The advancement of photolithography can be broadly attributed to the shortening of wavelengths of light sources used in exposure tools and the associated development of new photoresists. Photoresists are required to satisfy all of the following requirements: high resolution, low roughness, and high sensitivity. Conventional resists are photosensitive compositions containing organic polymer-based photoacid generators and are called chemically amplified resists. This resist promotes chemical reactions through the diffusion of acid. However, the acid diffusion process can cause line edge roughness (LER), resulting in reduced resolution, making them incompatible with ultrafine patterning.

[0003] In recent years, non-chemically amplified photoresists (hereinafter referred to as metal-containing resists) have been proposed, which are primarily composed of compounds containing metal elements such as Zn and Sn. In metal-containing resists, the metal component itself is the photosensitive substance and functions as the base material. Because they do not involve acid diffusion, they can improve line edge roughness, making them promising next-generation resist materials for forming finer pattern structures. In fact, it has been reported that finer patterns can be formed using next-generation exposure equipment using extreme ultraviolet (EUV) light.

[0004] For example, Patent Documents 1 to 6 and Non-Patent Documents 1 to 3 below disclose resist pattern formation methods using extreme ultraviolet rays (EUV light) or electron beams. ４ and endo-5-norbornene-2-carboxylic acid to obtain a compound [Zr ６ O ４ (OH) ４ (OOC-Norb) １２ However, the ligand of the resulting compound is bonded to the carboxylate group at carbon C １ The carbon C adjacent to ２ There is no disclosure of the compound having a specific substituent group or of using the compound as a metal-containing resist.

[0005] JP 2015-108781 A JP 2001-072716 A JP 2017-173537 A JP 2012-185484 A JP 2021-102604 A International Publication No. 2024 / 143204

[0006] Minoru Toriumi etc.,Proc.SPIE,9779(2016)97790GLianjia Wu etc.,Proc.SPIE,10957(2019)109570BNeha Thakur etc.,Proc.SPIE,10957(2019)10957DCoord. Chem. Rev., 2021, 438, Articles No. 213886, Pages 1-70J. Mater. Chem., 16 (2006) 5537-5539

[0007] In photolithography, particularly in semiconductor photolithography, there is a demand for photosensitive compositions and pattern formation methods that can realize even finer circuit patterns.

[0008] As a result of extensive research, the present inventors have found that compounds having specific structures are suitable as photoresists compatible with ultrafine patterns. Accordingly, an object of the present invention is to provide a compound or cluster compound suitable for a photosensitive composition capable of realizing fine circuit patterns, a photosensitive composition containing the compound or cluster compound, a pattern formation method using the photosensitive composition, a substrate having a pattern layer obtained by the pattern formation method, and a method for manufacturing the substrate.

[0009] The present invention has the following aspects [1] to

[31] .

[0010] [1] A compound containing a metal atom and a carboxylate ligand A having a cyclic structure, wherein the carboxylate ligand A has a cyclic structure bonded to a carboxylate group, and a carbon C in the cyclic structure bonded to the carboxylate group １ is a tertiary or quaternary carbon, and carbon C １ The carbon C adjacent to ２ is a substituent R １ and the substituent R １ is an organic group or a halogen atom.

[0011] [2] The compound according to [1], wherein the cyclic structure has a double bond.

[0012] [3] The compound according to [1] or [2], wherein the carboxylate ligand A is a ligand represented by the following general formula (1):

[0013] In the general formula (1), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 1 to 8, and in the ring structure, A ｎ is a substituent R ２and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 8, and ｎ is the substituent R ２ and has a substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is an integer of 0 to 2n.

[0014] [4] The substituent R in the general formula (1) １ is a hydrocarbon group or an ester group.

[0015] [5] The compound according to [3] or [4], wherein m in the general formula (1) is 0.

[0016] [6] The compound according to [1], wherein the carboxylate ligand A is a ligand represented by the following general formula (5):

[0017] In the general formula (5), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２and has a substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is the number of the cyclic structure and the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

[0018] [7] The substituent R in the general formula (5) １ is a hydrocarbon group or an ester group.

[0019] [8] The compound according to [6] or [7], wherein m in the general formula (5) is 0.

[0020] [9] The compound according to any one of [1] to [8], wherein the metal atom is a poor metal atom.

[0021]

[10] The compound according to [9], wherein the poor metal atom is at least one selected from bismuth and antimony.

[0022]

[11] The compound according to any one of [1] to

[10] , wherein the cyclic structure of the carboxylate ligand A is any one of a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, and a norbornane ring.

[0023]

[12] The compound according to [1], wherein the carboxylate ligand A is a ligand represented by the following general formula (2):

[0024] In formula (2), the substituent R ３ is any one of an alkyl group, a saturated alicyclic group, an unsaturated alicyclic group, and an aromatic group, and the substituent R ３ The hydrogen atoms of the formula (I) may be substituted with halogen atoms, and l represents the coordination number and is an integer of 1 to 3.

[0025]

[13] The compound according to claim [1], wherein the compound containing the metal atom and the carboxylate ligand A having a cyclic structure is represented by the following general formula (3):

[0026] In the general formula (3), M is the metal atom, and the substituent R ３ and substituent R ４are alkyl groups, saturated alicyclic groups, unsaturated alicyclic groups, or aromatic groups, and may be the same or different; ３ and substituent R ４ The structure of the compound (I) may contain an unsaturated hydrocarbon or a halogen atom. x is an integer of 1 to 3.

[0027]

[14] The substituent R in the general formula (3) ３ is a methyl group, and the substituent R ４ is a methylcyclohexenyl group.

[0028]

[15] The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (6):

[0029] In the general formula (6), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and the carbon C １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ and substituent R １ａ are each independently an organic group or a halogen atom, ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ or the substituent R １ａ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and the substituent R ２When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is the number of the cyclic structure and the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

[0030]

[16] . The substituent R in the general formula (6) １ or a substituent R １ａ are each independently a hydrocarbon group or an ester group.

[0031]

[17] The compound according to [1], wherein the carboxylate ligand A is a ligand represented by the following general formula (7):

[0032] In the general formula (7), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and the carbon C １ and the adjacent carbon C ２ The substituent R １ and substituent R １ｂ and the substituent R １ , the substituent R １ａ or the substituent R １ｂ are each independently an organic group or a halogen atom, ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ , substituent R １ａ or a substituent R １ｂ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and has a substituent R ２When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is the number of the cyclic structure and the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

[0033]

[18] . The substituent R in the general formula (7) １ , substituent R １ａ or a substituent R １ｂ are each independently a hydrocarbon group or an ester group.

[0034]

[19] A cluster compound, wherein the compound according to [1] is a compound having a plurality of the metal atoms, and the metal atoms have a metal-metal bond or are bonded to each other via 1 to 3 atoms.

[0035]

[20] The cluster compound according to

[19] , which contains the metal atom and the carboxylate ligand A represented by the following general formula (4):

[0036] In the general formula (4), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 1 to 8, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and the substituent R ２When is an alkylene group, it may be a polycyclic structure in which alkylene groups are crosslinked, and m is an integer of 0 to 2n. 1 represents the coordination number and is an integer of 1 to 3, and when it is 2 or more, the structures of the general formula (4) may be the same or different.

[0037]

[21] The cluster compound according to

[19] or

[20] , wherein the metal atom is a poor metal atom.

[0038]

[22] The cluster compound according to

[21] , wherein the poor metal atom is at least one selected from bismuth and antimony.

[0039]

[23] A method for producing the compound according to any one of [1] to

[18] , comprising reacting a compound containing a metal atom with a carboxylic acid having a carboxylate ligand A structure in a solution.

[0040]

[24] A photosensitive composition comprising at least one compound selected from the compounds according to any one of [1] to

[18] and the cluster compounds according to any one of

[19] to

[22] .

[0041]

[25] The photosensitive composition according to

[24] , further comprising a solvent.

[0042]

[26] A photosensitive composition comprising at least one compound selected from the group consisting of the compounds according to any one of [1] to

[18] and the cluster compounds according to any one of

[19] to

[22] , in a concentration of 50 to 100 mass percent of the total solids.

[0043]

[27] The photosensitive composition according to any one of

[24] to

[26] , which reacts with actinic radiation having a wavelength of 6 nm or more and 15 nm or less.

[0044]

[28] A pattern forming method comprising the steps of applying the photosensitive composition according to any one of

[24] to

[27] to a substrate, exposing the composition to actinic radiation, and developing the composition.

[0045]

[29] The pattern formation method according to

[28] , wherein the development is carried out using a developer, and the developer is an organic solvent having a solubility parameter (SP value) of 7.5 or more and 11 or less.

[0046]

[30] A substrate having a patterned layer obtained by the pattern forming method according to

[28] or

[29] .

[0047]

[31] A method for manufacturing a substrate in which a pattern layer is formed by the pattern forming method according to

[28] or

[29] .

[0048] The compound of the present invention is suitable as a photosensitive composition, is relatively easy to synthesize, and is suitable for mass production. It also has high sensitivity to extreme ultraviolet (EUV) light, high throughput, and high resolution, making it highly practical as a photoresist capable of forming ultrafine patterns. The compound of the present invention contains a carboxylate ligand A having a cyclic structure to which a substituent is bonded at a specific position, and is therefore presumed to be stable and resistant to deterioration even when stored for long periods of time. On the other hand, the bond between the carboxylate group and the cyclic structure is also susceptible to cleavage by actinic radiation such as electron beam (EB) irradiation or extreme ultraviolet (EUV) exposure. This cleavage, insolubilization in organic solvents, is presumed to result in the formation of a negative pattern, resulting in a photosensitive composition with excellent developability. Detailed Description of the Invention

[0049] The present invention will be described below based on one embodiment, but the present invention is not limited to this embodiment.

[0050] In addition, in this specification, there are some descriptions using "~" as a description expression to indicate a numerical range from a lower limit value to an upper limit value of a numerical value, but the numerical range in this description is a numerical range specified as being equal to or greater than the lower limit value and equal to or less than the upper limit value, including the lower limit value itself and the upper limit value itself.

[0051] [Compound] A compound according to one embodiment of the present invention (hereinafter also referred to as the present compound) contains a metal atom and a carboxylate ligand A having a cyclic structure. The cyclic structure refers to a chemical structure forming a single ring contained in an organic compound, and typical examples thereof include an alicyclic structure and a heterocyclic structure. The carboxylate ligand A has a cyclic structure that bonds to a carboxylate group, and the carbon C in the cyclic structure that bonds to the carboxylate group is １ is a tertiary or quaternary carbon, and carbon C １ The carbon C adjacent to ２ is a substituent R １ The substituent R １ is an organic group or a halogen atom. The organic group is any one of a hydrocarbon group such as an alkyl group or a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amino group, an amide group, and a carbonyl oxygen group, and the substituent R １ In the structure, hydrogen atoms may be substituted with halogen atoms.

[0052] The term "compound" refers to a metal complex molecule having a metal atom and a ligand, in which one or more metal atoms are bonded to each other directly or through a bridging ligand. This includes mononuclear and polynuclear complexes, and may take the form of either a complex compound or a cluster compound. The compound may contain oxygen and / or hydroxyl groups within its structure, preferably a μ-oxo ligand (—O—) in which an oxygen atom is coordinated between metal atoms and / or a μ-hydroxy ligand (—OH) in which a hydroxy group is coordinated to a metal. The term "cluster compound" as used herein refers to a compound containing multiple metal atoms, in which the metal atoms are bonded to each other via a metal-metal bond or one to three atoms between the metal atoms. The term "carboxylate ligand" refers to a ligand having at least one carboxylate group, and the carboxylate group is a functional group having the chemical structure -C(═O)O-.

[0053] The present compound contains a metal atom, and the metal atom may be a transition metal atom or a minor metal atom. The transition metal atom is preferably one or more selected from zirconium, hafnium, and titanium, and among these, zirconium or hafnium is preferred. Hafnium is an element in the same group as zirconium and has very similar chemical and physical properties.

[0054] The poor metal atom is an atom of a poor metal element, and a poor metal element refers to a metal or metalloid element that is in the P-block elements (elements with valence electrons in the outermost P orbital) on the periodic table. Compared to transition metals, they tend to have lower melting points and boiling points, higher electronegativity, and softer materials. Examples of poor metal elements include bismuth, antimony, aluminum, gallium, indium, thallium, tin, and lead. The poor metal atom of the present compound is preferably one or more selected from these elements, and among these, either bismuth or antimony is preferred from the viewpoints of high absorbance of actinic radiation and safety. Bismuth is more preferred, as it has a high mass number and high elemental density, resulting in high absorbance of actinic radiation such as extreme ultraviolet (EUV) light, which is proportional to elemental density.

[0055] The present compound contains a carboxylate ligand A, and this carboxylate ligand A has a cyclic structure bonded to a carboxylate group. It is believed that the coordinate bond between the metal atom and the carboxylate ligand A is resistant to hydrolysis by moisture or oxygen, resulting in stability that is resistant to deterioration even during long-term storage. The cyclic structure is preferably composed of 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and particularly preferably 3 to 7 carbon atoms. Examples of the cyclic structure include a saturated alicyclic structure, an unsaturated alicyclic structure, and a heterocyclic structure. Examples of the saturated alicyclic structure include a cyclopropane ring, a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, and a norbornane ring. Examples of the unsaturated alicyclic structure include a cyclopropene ring, a cyclopentene ring, a cyclobutene ring, a cyclohexene ring, and a norbornene ring.

[0056] In the cyclic structure of the carboxylate ligand A, one of the carbons constituting the cyclic structure is bonded to a carboxylate group, and the carbon C to which the carboxylate group is bonded is １ is a tertiary or quaternary carbon, and carbon C in the ring structure １ The carbon C adjacent to ２ Substituent R １ It has the following characteristics.

[0057] Substituent R 1 is not particularly limited, but is an organic group or a halogen atom. The organic group is preferably any one of a hydrocarbon group such as an alkyl group or a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group, and the organic group may contain a halogen atom or a heteroatom. １ The hydrogen atoms in the structure may be substituted with halogen atoms, and the structure may contain unsaturated hydrocarbons. 1 The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0058] Substituent R １Specific examples of the hydrocarbon group include linear alkyl groups such as methyl and ethyl groups, branched alkyl groups such as isopropyl and butyl groups, halogenated alkyl groups such as halogenated methyl groups, halogenated ethyl groups, and halogenated propyl groups, and cycloalkyl groups such as cyclopropyl and cyclobutyl groups. Examples of the aromatic group include aryl groups such as phenyl and naphthyl groups, arylalkyl groups, and alkylaryl groups. Examples of the organic group containing a heteroatom include ester groups, sulfonyl groups, alkoxy groups, amide groups, amino groups, and carbonyl oxygen groups. Examples of the ester group include alkyl ester groups such as acetyl groups, ethyl ester groups, and n-propyl ester groups, and aromatic ester groups such as phenyl ester groups. Examples of the sulfonyl group include methylsulfonyl groups, ethylsulfonyl groups, and n-propylsulfonyl groups. Examples of the alkoxy group include methoxy groups, ethoxy groups, n-propoxy groups, and phenoxy groups. Examples of the amino group include amino alkyl groups such as amino group (-NH2), aminomethyl group (NH2-CH2-), aminoethyl group (NH2-C2H4-), and aminopropyl group (NH2-C3H6-), and dialkylamino groups such as dimethylamino ((CH3)2N-) and diethylamino ((C2H5)2N-). Examples of the amide group include alkylamide groups such as methylamide group ((CH3)2N(C=O)-) and ethylamide group ((C2H5)2N(C=O)-). Examples of the carbonyl oxygen group (>C=O) include halogen atoms such as fluorine, chlorine, and bromine. The above substituent R １ In the specific examples of the above, the structure may contain an unsaturated hydrocarbon or a halogen atom. １ is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group.

[0059] More specifically, the carboxylate ligand A is preferably a ligand represented by the following general formula (1).

[0060]

[0061] In the general formula (1), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ Substituent R １ and has a substituent R １ is an organic group or a halogen atom. ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 1 to 8. In the ring structure, A ｎ is a substituent R ２ and may have a substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 8, and ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ are connected by a single bond, m is an integer of 0 to 2n.

[0062] The general formula (1) represents the carbon C to which the carboxylate group is bonded. １ and the adjacent carbon C ２ Substituent R １ In this case, carbon C １ is a tertiary carbon. １ is an organic group or a halogen atom, and the substituent R １ The hydrogen atoms in the structure of may be substituted with halogen atoms such as fluorine, chlorine, and bromine. １ Specific examples of the substituent R include those mentioned above. １ is preferably a hydrocarbon group or an ester group, which has the effect of approaching the metal element through weak interaction while preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. 1The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0063] In the above general formula (1), A ｎ is either a carbon or a heteroatom. １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 1 to 8. In the ring structure, A ｎ is a substituent R ２ A ｎ Examples of heteroatoms in C include oxygen, nitrogen, phosphorus, sulfur, and silicon. １ ,C ２ ,A ｎ The 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. An unsaturated ring structure is preferred, and A ｎ It is preferable that the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ The organic group can be selected from an alkyl group, a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group, and the substituent R １ n is an integer of 2 to 8, and may be the same as or different from A. ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When the substituents R are connected by a single bond, the substituent R is an integer of 0 to 2n. ２ Specific examples of the substituent R １ The substituent R ２ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R ２is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. １ approaches metal elements through weak interactions, while having the effect of preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. １ is an alkyl group, the substituent R ２ is an alkylene group, the substituent R １ and a substituent R ２ It is preferable that the compound does not form a polycyclic structure in which the substituents R are bridged. Furthermore, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in general formula (1) is preferably 1 to 7, more preferably 2 to 5. Similarly to n, from the viewpoints of solubility in a coating solvent and a developer and molecular size, m in general formula (1) is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0. When m=0, the substituent R ２ Therefore, the system will not have the following characteristics.

[0064] The carboxylate ligand A may be a ligand represented by the following general formula (5), which is preferred for ease of production.

[0065] In the general formula (5), the carbon C to which the carboxylate group A is bonded １ and the adjacent carbon C ２ Substituent R １ and has a substituent R １ is an organic group or a halogen atom. ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ and may have a substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ n is an integer of 2 to 7, and may be the same as or different from A.ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When they are connected by a single bond, it is an integer of 0 to 2n.

[0066] The general formula (5) represents the carbon C to which the carboxylate group is bonded. １ and the adjacent carbon C ２ Substituent R １ In this case, carbon C １ is a tertiary carbon. Also, carbon C １ and the other adjacent carbon C ３ has no substituent. １ is either an organic group or a halogen atom, and the substituent R １ The hydrogen atoms in the structure of may be substituted with halogen atoms such as fluorine, chlorine, and bromine. １ Specific examples of the substituent R １ The substituent R １ is preferably a hydrocarbon group or an ester group, which has the effect of approaching the metal element through weak interaction while preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. 1 The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0067] In the above general formula (5), A ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ A ｎ Examples of heteroatoms in C include oxygen, nitrogen, phosphorus, sulfur, and silicon. １ ,C ２ ,Aｎ The 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. An unsaturated ring structure is preferred, and A is more preferred. ｎ It is preferable that the substituent R ２ are each independently an organic group or a halogen atom, and the substituent R １ The organic group can be selected from an alkyl group, a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group. n is an integer of 2 to 8, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When the substituents R are connected by a single bond, the substituent R is an integer of 0 to 2n. ２ Specific examples of the substituent R １ The substituent R ２ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R ２ is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. １ approaches metal elements through weak interactions, while having the effect of preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. １ is an alkyl group, the substituent R ２ is an alkylene group, the substituent R １ and a substituent R ２It is preferable that the compound does not form a polycyclic structure in which the substituents R are bridged. In addition, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in general formula (5) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoints of solubility in a coating solvent and a developer and molecular size, m in general formula (5) is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0. When m=0, the substituent R ２ Therefore, the system will not have the following characteristics.

[0068] The carboxylate ligand A may be a ligand represented by the following general formula (6), which is preferred from the viewpoint of ease of production.

[0069]

[0070] In the general formula (6), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and carbon C １ and the adjacent carbon C ２ Substituent R １ and has a substituent R １ or a substituent R １ａ are each independently an organic group or a halogen atom. ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ n is an integer of 2 to 7, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When they are connected by a single bond, it is an integer of 0 to 2n.

[0071] The general formula (6) represents the carbon C to which the carboxylate group is bonded. １ and the adjacent carbon C ２Substituent R １ Carbon C １ is a quaternary carbon, and the substituent R １ａ Also, carbon C １ and the other adjacent carbon C ３ has no substituent. １ or a substituent R １ａ are each independently an organic group or a halogen atom. １ or a substituent R １ａ The hydrogen atoms in the structure of may be substituted with halogen atoms such as fluorine, chlorine, and bromine. １ or a substituent R １ａ Specific examples of the substituent R １ The substituent R １ is preferably a hydrocarbon group or an ester group, which has the effect of approaching the metal element through weak interaction while preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. 1 The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. １ａ has electron donating properties, and upon exposure, C １ A hydrocarbon group is preferred from the viewpoint that the bond between the carbonyl carbon adjacent to the substituent R and the carbonyl carbon adjacent to the substituent R is easily cleaved and the exposure sensitivity is increased. １ａ The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0072] In the above general formula (6), A ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. ｎ Examples of heteroatoms in C include oxygen, nitrogen, phosphorus, sulfur, and silicon. １ ,C ２ , C ３ ,A ｎThe 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. １ ,C ２ , C ３ ,A ｎ In the cyclic structure of ｎ is a substituent R ２ and may have a substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ or a substituent R １ａ The organic group can be selected from an alkyl group, a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group. n is an integer of 2 to 8, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ｎ and substituent R ２ When the substituents R are connected by a single bond, the substituent R is an integer of 0 to 2n. ２ Specific examples of the substituent R １ The substituent R ２ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R ２ is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. １ approaches metal elements through weak interactions, while having the effect of preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. １ is an alkyl group, the substituent R １ａ or a substituent R ２ is an alkylene group, the substituent R １ and a substituent R １ａ or a substituent R ２It is preferable that the compound does not form a polycyclic structure in which the substituents R are bridged. In addition, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in general formula (6) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoints of solubility in a coating solvent and a developer and molecular size, m in general formula (6) is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0. When m=0, the substituent R ２ Therefore, the system will not have the following characteristics.

[0073] The carboxylate ligand A may be a ligand represented by the following general formula (7), which is preferred from the viewpoint of ease of production.

[0074]

[0075] In the general formula (7), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and the carbon C １ and the adjacent carbon C ２ Substituent R １ and substituent R １ｂ The substituent R １ , substituent R １ａ or a substituent R １ｂ are each independently an organic group or a halogen atom. ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ n is an integer of 2 to 7, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When they are connected by a single bond, it is an integer of 0 to 2n.

[0076] The general formula (7) represents the carbon C to which the carboxylate group is bonded. １ and the adjacent carbon C ２ Substituent R １ and substituent R １ｂ Carbon C １ is a quaternary carbon, and the substituent R １ａ Also, carbon C １ and the other adjacent carbon C ３ has no substituent. １ , substituent R １ａ or a substituent R １ｂ are each independently an organic group or a halogen atom. １ , substituent R １ａ or a substituent R １ｂ The hydrogen atoms in the structure of may be substituted with halogen atoms such as fluorine, chlorine, and bromine. １ , substituent R １ａ or a substituent R １ｂ Specific examples of the substituent R １ The substituent R １ is preferably a hydrocarbon group or an ester group, which has the effect of approaching the metal element through weak interaction while preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. 1 The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. １ａ has electron donating properties, and upon exposure, C １ A hydrocarbon group is preferred from the viewpoint that the bond between the carbonyl carbon adjacent to the substituent R and the carbonyl carbon adjacent to the substituent R is easily cleaved and the exposure sensitivity is increased. １ａ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. １ｂ is preferably a hydrocarbon group in terms of molecular size and in terms of inhibiting the approach of water molecules to prevent unnecessary hydrolysis, and the substituent R １ｂ The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0077] In the above general formula (7), A ｎis either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ A ｎ Examples of heteroatoms in C include oxygen, nitrogen, phosphorus, sulfur, and silicon. １ ,C ２ , C ３ ,A ｎ The 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. An unsaturated ring structure is preferred, and A ｎ It is preferable that the compound has an unsaturated bond at the site represented by C. １ ,C ２ , C ３ ,A ｎ In the cyclic structure of ｎ is a substituent R ２ and may have a substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ , substituent R １ａ or a substituent R １ｂ The organic group can be selected from an alkyl group, a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group. n is an integer of 2 to 8, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When these substituents R are connected by a single bond, it is an integer of 0 to 2n. ２ Specific examples of the substituent R １ The substituent R ２The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R ２ is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. １ approaches metal elements through weak interactions, while having the effect of preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. １ is an alkyl group, the substituent R １ａ , substituent R １ｂ or a substituent R ２ is an alkylene group, the substituent R １ and a substituent R １ａ , substituent R １ｂ or a substituent R ２ It is preferable that the compound does not form a polycyclic structure in which the substituents R are bridged. In addition, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in general formula (7) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoints of solubility in a coating solvent and a developer and molecular size, m in general formula (7) is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0. When m=0, the substituent R ２ Therefore, the system will not have the following characteristics.

[0078] The carboxylate ligand A may be a ligand represented by the following general formula (8), which is preferred from the viewpoint of ease of production.

[0079]

[0080] In the general formula (8), the carbon C to which the carboxylate group A is bonded １ and the adjacent carbon C ２ Substituent R １ and the carbon C １ and the adjacent carbon C ３ Substituent R １ｃ and has a substituent R １ or a substituent R １ｃ are each independently an organic group or a halogen atom. ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C１ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, and n is an integer of 0 to 7. In the ring structure, A ｎ is a substituent R ２ n is an integer of 2 to 7, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When they are connected by a single bond, it is an integer of 0 to 2n.

[0081] The general formula (8) represents the carbon C to which the carboxylate group A is bonded. １ and the adjacent carbon C ２ Substituent R １ Carbon C １ is a tertiary carbon. Also, carbon C １ and the other adjacent carbon C ３ is a substituent R １ｃ The substituent R １ or a substituent R １ｃ are each independently an organic group or a halogen atom. １ or a substituent R １ｃ The hydrogen atoms in the structure of may be substituted with halogen atoms such as fluorine, chlorine, and bromine. １ or a substituent R １ｃ Specific examples of the substituent R １ The substituent R １ is preferably a hydrocarbon group or an ester group, which has the effect of approaching the metal element through weak interaction while preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. 1 The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. １ｃ is preferably a hydrocarbon group in terms of molecular size and in terms of inhibiting the approach of water molecules to prevent unnecessary hydrolysis, and the substituent R １ｃThe number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0082] In the above general formula (8), A ｎ Examples of heteroatoms in C include oxygen, nitrogen, phosphorus, sulfur, and silicon. １ ,C ２ , C ３ ,A ｎ The 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. An unsaturated ring structure is preferred, and A ｎ It is preferable that the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ or a substituent R １ｃ The organic group can be selected from an alkyl group, a cycloalkyl group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group, and the substituent R １ or a substituent R １ｃ may be the same as or different from each other. n is an integer of 2 to 8, and ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ When these substituents R are connected by a single bond, they are integers of 0 to 2n. ２ Specific examples of the substituent R １ The substituent R ２ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R ２ is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. １approaches metal elements through weak interactions, while having the effect of preventing water molecules from approaching from the outside, making it less susceptible to hydrolysis and providing excellent long-term stability. １ is an alkyl group, the substituent R １ｃ or a substituent R ２ is an alkylene group, the substituent R １ and a substituent R ２ or a substituent R １ｃ It is preferable that the compound does not form a polycyclic structure in which the substituents R are bridged. In addition, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in general formula (8) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoints of solubility in a coating solvent and a developer and molecular size, m in general formula (8) is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0. When m=0, the substituent R ２ Therefore, the system will not have the following characteristics.

[0083] The carboxylate ligand A may be represented by the following general formula (2), which is preferred in terms of ease of production and development speed in a developer.

[0084]

[0085] In the above general formula (2), the substituent R ３ is any one of an alkyl group, a saturated alicyclic group, an unsaturated alicyclic group, and an aromatic group, and the substituent R ３ The hydrogen atoms in the formula (I) may be substituted with halogen atoms. 1 represents the coordination number and is an integer of 1 to 3.

[0086] Substituent R 3 Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group; examples of the saturated alicyclic group include a cyclopropanoyl group, a cyclobutanoyl group, a cyclopentanoyl group, and a cyclohexanoyl group; and examples of the unsaturated alicyclic group include a cyclopropenyl group, a cyclopentenyl group, a cyclobutenyl group, a cyclohexenyl group, and a norbornene group. Examples of the aromatic group include a phenyl group and a naphthyl group. Substituent R ３ The number of carbon atoms of the substituent R is preferably 1 to 10, more preferably 1 to 5. ３is preferably an alkyl group or an aromatic group, more preferably an alkyl group.

[0087] The structure of the carboxylate ligand A can be analyzed by known methods, for example, by NMR. Furthermore, in the present compound, multiple different carboxylate ligands A can be used simultaneously. When the carboxylate ligand A is replaced with (meth)acrylic acid, there tends to be room for improvement in terms of film formability. Furthermore, when the carboxylate ligand of the present compound is replaced with an aromatic carboxylic acid such as benzoic acid, there tends to be room for improvement in terms of exposure sensitivity and solvent solubility.

[0088] The present compound preferably has a structure represented by the following general formula (3) in terms of ease of production and development speed in a developer.

[0089]

[0090] In the general formula (3), M is the metal atom, and the substituent R ３ means the substituent R shown in the general formula (2) above. ３ and the substituent R ４ is an alkyl group, a saturated alicyclic group, an unsaturated alicyclic group, or an aromatic group, and the substituent R ３ and substituent R ４ may be the same or different, and the substituent R ３ and substituent R ４ The structure of the formula (I) may contain an unsaturated hydrocarbon or a halogen atom. x is an integer of 1 to 3.

[0091] Substituent R ４In the above, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group; examples of the saturated alicyclic group include a cyclopropanoyl group, a cyclobutanoyl group, a cyclopentanoyl group, a cyclohexanoyl group, a methylcyclohexanoyl group, and a cyclopropenyl group; examples of the unsaturated cyclic group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, and a methylcyclohexenyl group; and examples of the aromatic group include a phenyl group and a naphthyl group. ４ is preferably a methylcyclohexenyl group. ４ The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 3 to 10. ４ is preferably an alkyl group, a saturated alicyclic group, or an unsaturated alicyclic group, and more preferably a saturated alicyclic group or an unsaturated alicyclic group. ４ is a saturated alicyclic group or an unsaturated alicyclic group, the substituent R ４ Carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ Substituent R １ is preferably bonded to the substituent R １ is the same as above.

[0092] The compound may be in the form of a cluster compound, as described above.

[0093] Preferably, the cluster compound contains the metal atom and the carboxylate ligand A represented by the following general formula (4).

[0094]

[0095] In the above general formula (4), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ Substituent R １ and has a substituent R １ is an organic group or a halogen atom. ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎconstitutes a 3- to 10-membered ring structure, and n is an integer of 1 to 8. In the ring structure, A ｎ is a substituent R ２ and may have a substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ The substituent R may be the same as or different from １ or a substituent R ２ is the above-mentioned substituent R １ or a substituent R ２ n is an integer of 2 to 8, and a plurality of A ｎ is the substituent R ２ and has a substituent R ２ When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. ２ are connected by a single bond, it is an integer of 0 to 2n. In general formula (4), m is also preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0, from the viewpoint of solubility in coating solvents and developing solutions and molecular size. When m=0, the substituent R ２ l represents the coordination number and is an integer of 1 to 3. When l is 2 or more, the l structures contained in general formula (4) may be the same or different.

[0096] The molecular weight of this compound is preferably 100 to 8,000, more preferably 200 to 8,000, and particularly preferably 300 to 7,000. When this compound is in the form of a mononuclear complex, the molecular weight is preferably 100 to 1,000, more preferably 200 to 800, and particularly preferably 300 to 700. When this compound is in the form of a cluster compound, the molecular weight is preferably 1,000 to 10,000, more preferably 1,000 to 8,000, and particularly preferably 1,500 to 7,000. If the molecular weight of this compound is below the above upper limit, the volume is small, and roughness and resolution are expected to be improved. On the other hand, if the molecular weight is above the above lower limit, coating properties and etching resistance tend to be improved. Note that this molecular weight is a guideline and does not determine lithography properties by itself, so it is not limited to this. The molecular weight of this compound can be analyzed by known techniques, for example, NMR.

[0097] [Production Method] The present compound can be produced, for example, by reacting a compound containing a metal atom with a carboxylic acid having a carboxylate ligand A structure. For example, the compound can be produced by reacting a solution containing a compound containing a metal atom with a carboxylic acid having a carboxylate ligand A structure in solution. Furthermore, when synthesizing a compound having a non-metallic metal atom and two different carboxylate ligands A, the compound can also be produced, for example, by reacting a solution containing a compound containing a non-metallic metal atom described below with a carboxylic acid having a carboxylate ligand A1 structure and a carboxylic acid having a carboxylate ligand A2 structure different from the carboxylate ligand A1 structure.

[0098] When the compound containing a metal atom is a compound containing a transition metal atom, examples of the metal atom include zirconium, hafnium, or titanium, and examples of the compound include alkoxides of transition metal elements such as zirconium propoxide, zirconium n-butoxide, zirconium 2-ethylhexoxide, hafnium propoxide, hafnium n-butoxide, hafnium 2-ethylhexoxide, titanium propoxide, titanium n-butoxide, and titanium 2-ethylhexoxide. When the compound is a compound containing a minor metal atom, examples of the metal atom include bismuth and antimony, and examples of this compound include organic compounds containing minor metals, specifically trisphenylbismuth, tris-paratoluylbismuth, trisphenylantimony, and tris-paratoluylantimony.

[0099] Examples of carboxylic acids having the structure of a carboxylate ligand A include the above-described carboxylic acids having the structure of a carboxylate ligand A. The carboxylic acid exemplified by the following chemical formula (5) has a saturated alicyclic structure composed of six carbon atoms, in which the carbon atom in the saturated alicyclic structure that bonds to the carboxylic acid of the carboxylate group is tertiary, and has an ethyl ester group on one of the carbon atoms adjacent to the tertiary carbon.

[0100]

[0101] Furthermore, examples of carboxylic acids having a structure of a carboxylate ligand A include carboxylic acids having a structure represented by the above general formula (1), (2), or (3). More specifically, 2-methylcyclohexane-1-carboxylic acid, 2-ethylcyclohexane-1-carboxylic acid, 2-normal propylcyclohexane-1-carboxylic acid, 2-cyclohexylcyclohexane-1-carboxylic acid, 2-phenylcyclohexane-1-carboxylic acid, 2-methoxycyclohexane-1-carboxylic acid, 2-ethoxycyclohexane-1-carboxylic acid, 2-normal propoxycyclohexane-1-carboxylic acid, 2-methyl ester cyclohexane-1-carboxylic acid, 2-ethyl ester cyclohexane-1-carboxylic acid, 2-normal propyl ester cyclohexane-1-carboxylic acid, 2-methylsulfonic acid ester cyclohexane-1-carboxylic acid, 2-ethylsulfonic acid ester cyclohexane-1-carboxylic acid, 2-normal propyl sulfonic acid ester cyclohexane-1-carboxylic acid, 2-(N-methylamido)cyclohexane-1-carboxylic acid, 2-fluorocyclohexa cyclohex-3-ene-1-carboxylic acid, 2-chlorocyclohexane-1-carboxylic acid, 2-bromocyclohexane-1-carboxylic acid, 6-methylcyclohex-3-ene-1-carboxylic acid, 6-ethylcyclohex-3-ene-1-carboxylic acid, 6-normal propylcyclohex-3-ene-1-carboxylic acid, 6-methoxycyclohex-3-ene-1-carboxylic acid, 6-ethoxycyclohex-3-ene-1-carboxylic acid, 6-normal propoxycyclohex-3-ene-1-carboxylic acid, 6-ethyl ester cyclohex-3-ene-1-carboxylic acid, 6-methyl ester cyclohex-3-ene-1-carboxylic acid, 6-normal propyl ester cyclohex-3-ene-1-carboxylic acid, 6-methylsulfonic acid ester cyclohex-3-ene-1-carboxylic acid, 6-ethylsulfonic acid ester cyclohex-3-ene-1-carboxylic acid, 6-normal propylsulfonic acid ester cyclohex-3-ene-1-carboxylic acid, 6-(N-methylamido)cyclohex-3-ene-1-carboxylic acid, 6-fluorocyclohex-3-ene-1-carboxylic acid, 6-chlorocyclohex-3-ene-1-carboxylic acid,Examples include 6-bromocyclohex-3-ene-1-carboxylic acid, 3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, 6-methoxycarbonyl-1,3,4,6-tetramethyl-cyclohex-3-ene-1-carboxylic acid, 6-methyl-3-cyclohexene-1-carboxylic acid, and 1,6-dimethyl-3-cyclohexene-1-carboxylic acid.

[0102] To explain the production method in more detail, the solution containing the compound containing the poor metal atom and the carboxylic acid having the structure of carboxylate ligand A are placed in a reaction vessel and stirred. A solvent may be added to dissolve the raw materials.

[0103] The reaction temperature is preferably room temperature to 150°C, more preferably room temperature to 120°C, from the viewpoint of completing the reaction and preventing undesirable side reactions. The reaction time is preferably 1 to 100 hours, more preferably 3 to 24 hours. If the product precipitates or crystallizes after the reaction, the compound can be obtained by filtration. The post-reaction solution may be cooled to -30°C to 20°C to obtain the product precipitate or crystals. If no product precipitate is observed after the reaction, the target product can be recovered by distilling off the solvent by applying reduced pressure to the reaction vessel. Alternatively, the product can be reprecipitated by contacting the reaction solution with a poor solvent. A sealed reaction vessel is preferred, and for small volumes, a Schlenk tube or the like can be used. The reaction is preferably carried out under a nitrogen or argon atmosphere. A flask equipped with a reflux condenser is preferred as the reaction vessel, and the reaction is preferably carried out under a nitrogen or argon atmosphere when heated.

[0104] The solution containing the compound containing a metal atom and the carboxylic acid having a structure of carboxylate ligand A are preferably mixed in a molar ratio of 1:1 to 1:3, more preferably 1:3. When synthesizing a compound having a poor metal atom and two different carboxylate ligands A, if the compound obtained in the above step is a compound having carboxylate ligand A1, for example, a compound having a poor metal atom and carboxylate ligands A1 and A2 can be obtained by heating and stirring a solution containing carboxylate ligand A1 and a compound containing a poor metal atom and carboxylate ligand A2 in a similar reaction vessel.

[0105] [Photosensitive Composition] A photosensitive composition according to one embodiment of the present invention (hereinafter also referred to as the present photosensitive composition) contains the present compound. The present photosensitive composition may contain only one type of the present compound, or may contain two or more types of the present compound.

[0106] The present photosensitive composition contains the present compound in a concentration of 50 to 100 mass percent, preferably 60 to 100 mass percent, and particularly preferably 70 to 90 mass percent, of total solids relative to the total of all components of the photosensitive composition other than the solvent. The term "total solids" refers to the solid obtained by evaporating the photosensitive composition to dryness. The concentration of the present compound in the present photosensitive composition is preferably 0.1 mass% to 70 mass%; more preferably 0.5 mass% to 50 mass%; and particularly preferably 1 mass% to 40 mass%. When the concentration of the present compound in the present photosensitive composition is equal to or higher than the lower limit, good exposure sensitivity can be obtained.

[0107] [Photoacid Generator] The photosensitive composition can also function by containing, together with the compound, a photoacid generator that generates an acid by the action of actinic radiation. Examples of actinic radiation include the bright line spectrum of a mercury lamp, far ultraviolet radiation represented by an excimer laser, extreme ultraviolet radiation (EUV light), X-rays, and electron beams. From the viewpoint of resolution, a shorter exposure wavelength is preferred, and extreme ultraviolet radiation (EUV light) emitting light with a wavelength of 6 nm or more and 15 nm or less is preferred.

[0108] The photoacid generator that generates an acid when exposed to actinic radiation is not particularly limited as long as it is a known compound, but is preferably a compound that generates an organic acid, such as at least one of sulfonic acid, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide, when exposed to actinic radiation.

[0109] The photoacid generators can be used alone or in combination of two or more. When two or more types are used in combination, preferred embodiments include (1) the use of two photoacid generators with different acid strengths, and (2) the use of two photoacid generators with different sizes (molecular weights or carbon numbers) of the acids they generate. Examples of the embodiment (1) include the use of a fluorine-containing sulfonic acid generator and a tris(fluoroalkylsulfonyl)methide acid generator, a fluorine-containing sulfonic acid generator and a non-fluorine-containing sulfonic acid generator, and an alkylsulfonic acid generator and an arylsulfonic acid generator. Examples of the embodiment (2) include the use of two photoacid generators whose acid anions differ in the number of carbon atoms by four or more.

[0110] In particular, the present photosensitive composition is preferably a photosensitive composition for use with actinic radiation. A photosensitive composition that reacts with actinic radiation is preferred because the development speed in a developer changes, allowing a pattern to be formed after a certain period of development. As actinic radiation, a shorter wavelength is preferred because higher resolution can be obtained. Actinic radiation with a wavelength of 6 nm or more and 15 nm or less is preferred, and more preferably actinic radiation with a wavelength of 6.5 nm or more and 13.5 nm or less is preferred. In other words, extreme ultraviolet (EUV) light is preferred. In other words, the present photosensitive composition is preferably a photosensitive composition that reacts with actinic radiation with a wavelength of 6 nm or more and 15 nm or less. The term "reaction" refers to the photosensitive composition absorbing the irradiated actinic radiation and then being modified by the generated active species, such as radicals and ions.

[0111] The present compound reacts with light even when used alone in a photosensitive composition. Adding a photoacid generator synergistically enhances the photosensitivity of the present compound in the photosensitive composition. Therefore, adding a photoacid generator is preferable when a photosensitive composition composed solely of the present compound does not have sufficient photosensitivity for the required specifications. When the present photosensitive composition contains a photoacid generator, the content of the photoacid generators in the present photosensitive composition (the total amount when multiple photoacid generators are used) is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and even more preferably 1 to 15% by mass, based on the total components of the photosensitive composition other than the solvent. When the content of the photoacid generator in the photosensitive composition is at or above the lower limit, the effect of enhancing photosensitivity is obtained. When the content is at or below the upper limit, the composition is less susceptible to the poor film-forming properties of the photoacid generator, thereby achieving good film-forming properties based on the photosensitive compound of the present invention, which is preferable.

[0112] [Solvent] The present photosensitive composition usually contains a solvent for preparing the composition. The solvent for preparing the photosensitive composition is not particularly limited as long as it dissolves each component, and examples thereof include toluene, alkylene glycol monoalkyl ether carboxylates (such as propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane)), alkylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)), alkyl lactate esters (such as ethyl lactate and methyl lactate), cyclic lactones (such as γ-butyrolactone, preferably having 4 to 10 carbon atoms), linear or cyclic ketones (such as 2-heptanone and cyclohexanone, preferably having 4 to 10 carbon atoms), alkylene carbonates (such as ethylene carbonate and propylene carbonate), alkyl carboxylates (preferably alkyl acetates such as butyl acetate), alkyl alkoxyacetates (ethyl ethoxypropionate), alkylamides (N,N-dimethylformamide), and alkyl sulfoxides (dimethyl sulfoxide). Other usable solvents include, for example, the solvents described in paragraphs

[0244] and after of US Patent Application Publication No. 2008 / 0248425A1.

[0113] Of the above, toluene, PGMEA, ethyl lactate, cyclohexanone, 2-heptanone, N,N-dimethylformamide, dimethyl sulfoxide, alkylene glycol monoalkyl ether carboxylate, and alkylene glycol monoalkyl ether are preferred.

[0114] These solvents may be used alone or in combination of two or more. When two or more solvents are mixed, it is preferable to mix a solvent having a hydroxyl group with a solvent not having a hydroxyl group. As the solvent having a hydroxyl group, alkylene glycol monoalkyl ether is preferred, and as the solvent not having a hydroxyl group, alkylene glycol monoalkyl ether carboxylate, N,N-dimethylformamide, and dimethyl sulfoxide are preferred.

[0115] The solvent for the present photosensitive composition preferably has a solubility parameter (SP value) of 7.5 or more and 11 or less, and more preferably 8 or more and 11 or less. The solubility parameter (SP value) will be described later.

[0116] The content of the solvent in the total amount of the photosensitive composition can be adjusted as appropriate depending on the film thickness of the pattern to be formed, etc., but is generally adjusted so that the total concentration of components other than the solvent in the photosensitive composition is 0.5 to 30 mass %, preferably 1.0 to 20 mass %, more preferably 1.5 to 10 mass %, and particularly preferably 1.5 to 5 mass %.

[0117] [Surfactant] The photosensitive composition preferably further contains a surfactant. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of such surfactants include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, Inc., PF656 and PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., Fluorad FC430 manufactured by Sumitomo 3M Limited, and Polysiloxane Polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd. Surfactants other than fluorine-based and / or silicone-based surfactants can also be used. More specifically, examples include polyoxyethylene alkyl ethers and polyoxyethylene alkylaryl ethers.

[0118] Other known surfactants may also be used as appropriate. Examples of usable surfactants include those described in paragraphs

[0273] and after in U.S. Patent Application Publication No. 2008 / 0248425A1.

[0119] The surfactant may be used alone or in combination of two or more kinds. The content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total mass of the components other than the solvent in the photosensitive composition.

[0120] [Resin] The photosensitive composition can be used alone to form a pattern, but it may also contain a resin material in addition to the compound. Resin materials are not particularly limited as long as they are soluble in a solvent, and examples include novolac resins, styrene resins, and acrylic resins. They may be used alone or in combination of two or more types. Their molecular structure may contain dissolution-inhibiting groups that decompose in the presence of chemically active species such as acids or radicals, or crosslinking groups that crosslink, or they may be copolymer resins of two or more types. Examples of dissolution-inhibiting groups that decompose in the presence of chemically active species such as acids or radicals include alkoxycarbonyl groups and acetal groups. Examples of crosslinking groups that crosslink in the presence of chemically active species such as acids or radicals include vinyl groups, carbodiimide groups, N-hydroxyester groups, imide ester groups, maleimide groups, haloacetyl groups, pyridyl disulfide groups, hydrazide groups, alkoxyamino groups, and diazirine groups.

[0121] [Other Additives] In addition to the components described above, the photosensitive composition may contain, as appropriate, carboxylic acids, carboxylic acid onium salts, dissolution-inhibiting compounds with a molecular weight of 3,000 or less as described in, for example, Proceedings of SPIE, 2724, 355 (1996), dyes, plasticizers, photosensitizers, light absorbers, crosslinking agents, antioxidants, and the like. Carboxylic acids are particularly preferred for improving performance. Preferred carboxylic acids include aromatic carboxylic acids such as benzoic acid and naphthoic acid. The carboxylic acid content is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, based on the total weight of the components of the photosensitive composition other than the solvent.

[0122] [Method for producing the present photosensitive composition] The present photosensitive composition can be produced by dissolving the present compound, a photoacid generator (if used) and other components in a solvent for preparation, and filtering the solution through a filter, if necessary. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon, and has a pore size of 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less.

[0123] [Pattern Forming Method] A pattern forming method according to one embodiment of the present invention (hereinafter also referred to as the present pattern forming method) comprises the steps of applying the present photosensitive composition to a substrate, exposing to actinic radiation, and developing. More specifically, it comprises the steps of applying the present photosensitive composition to a substrate to form a photosensitive layer, irradiating predetermined regions of the photosensitive layer with actinic radiation to perform pattern exposure, and developing the exposed photosensitive layer to selectively remove exposed or unexposed regions of the photosensitive layer. The photosensitive layer forming step provides a substrate having a photosensitive layer. The pattern exposure step provides a substrate with a latent image. The development step provides a substrate having a pattern layer.

[0124] [Photosensitive Layer Formation Step] The photosensitive layer can be formed by applying the photosensitive composition to a substrate (e.g., silicon or silicon dioxide coated) such as those used in the manufacture of integrated circuit devices using a suitable coating method such as a spinner, followed by drying at 50 to 150°C. In this case, a commercially available inorganic or organic antireflective film can be used, if necessary. Furthermore, an antireflective film can be applied as an underlayer of the resist.

[0125] [Exposure Step] In the present invention, unless otherwise specified, "exposure to actinic radiation" includes not only exposure with far ultraviolet light typified by mercury lamps and excimer lasers, X-rays, extreme ultraviolet light (EUV light), and the like, but also exposure with particle beams such as electron beams and ion beams. Exposure can be performed by irradiating predetermined regions of the formed photosensitive layer with actinic radiation through a predetermined mask to perform pattern exposure, or by irradiating with an electron beam to perform pattern exposure without using a mask (direct writing). The actinic radiation is not particularly limited, but examples include KrF excimer lasers, ArF excimer lasers, extreme ultraviolet light (EUV light), and electron beams. Extreme ultraviolet light (EUV light) and electron beams are preferred, and as described above, extreme ultraviolet light (EUV light) emitting actinic radiation with a wavelength of 6 nm to 15 nm is preferred.

[0126] After the exposure, baking (heating) may or may not be performed before development. When baking (heating) is performed, the heating temperature is preferably 50 to 200°C, more preferably 60 to 180°C, and even more preferably 80 to 150°C. When baking (heating) is performed, the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

[0127] [Development Step] After exposure, development is carried out to selectively remove the exposed or unexposed areas of the photosensitive layer. As the development method, a known method can be adopted, for example, a method using a gas or a method using a developer.

[0128] <Developer> It is preferable to use an organic solvent as the developer, and an organic solvent having a vapor pressure of 5 kPa or less at 20° C. is preferred, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, improving the temperature uniformity within the surface of the pattern-formed substrate, and as a result, improving the dimensional uniformity within the surface of the pattern-formed substrate.

[0129] As the organic solvent used as the developer, various organic solvents can be used, and for example, at least one solvent selected from ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, sulfoxide-based solvents, ether-based solvents, hydrocarbon-based solvents, and the like can be used.

[0130] Examples of ester-based solvents include alkyl carboxylate solvents such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl-3-ethoxypropionate, propylene glycol diacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate; alkylene glycol monoalkyl ether carboxylate solvents such as propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether acetate; and butyl acetate, amyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate are more preferred.

[0131] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate. Alkyl ketone solvents, such as methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone, are more preferred.

[0132] Examples of alcohol-based solvents include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol including 1-propanol or 2-propanol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, hexyl alcohols such as n-hexyl alcohol, heptyl alcohols such as n-heptyl alcohol, octyl alcohols such as n-octyl alcohol, and n-decanol; and glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol. alkylene glycol monoalkyl ether-based solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; glycol ether-based solvents such as methoxymethylbutanol and propylene glycol dimethyl ether; and phenol-based solvents such as phenol and cresol, with 1-hexanol, 2-hexanol, 1-octanol, 2-ethylhexanol, propylene glycol monomethyl ether, and cresol being more preferred.

[0133] Examples of the amide solvent that can be used include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, etc. Examples of the sulfoxide solvent that can be used include dimethyl sulfoxide, etc.

[0134] Examples of the ether solvent include the alkylene glycol monoalkyl ether solvents and glycol ether solvents described above, as well as dioxane, tetrahydrofuran, tetrahydropyran, and the like.

[0135] Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and dodecane.

[0136] The developer preferably contains one or more solvents selected from alkylene glycol monoalkyl ether carboxylate solvents, alkylene glycol monoalkyl ether solvents, alkyl carboxylate solvents, and alkyl ketone solvents, and more preferably contains one or more solvents selected from dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethylene glycol, methyl alcohol, ethyl alcohol, 1-propanol, and 2-propanol.

[0137] As the developer, it is preferable to use a developer containing at least one organic solvent selected from the group consisting of ester solvents having no hydroxyl group in the molecule, ketone solvents having no hydroxyl group in the molecule, and ether solvents having no hydroxyl group in the molecule, amide solvents, and sulfoxide solvents.

[0138] The organic solvent used as the developer in the present invention is preferably an organic solvent having a solubility parameter (SP value) of 7.5 or more and 11 or less. An organic solvent with a solubility parameter of 7.5 or more increases the development rate of the dissolved portion, while an organic solvent with a solubility parameter of 11 or less can suppress the development rate of the pattern formation portion, so these are preferred. The solubility parameter of the organic solvent of the developer is more preferably 8 or more and 11 or less.

[0139] In the present invention, the solubility parameter (SP value) is calculated by the method proposed by Fedors et al. Specifically, the value is determined by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)." The SP value is a physical property determined by the content of hydrophobic and hydrophilic groups in the molecule, and when a mixed solvent is used, the SP value refers to the value of the mixture.

[0140] Examples of organic solvents that satisfy the above SP values ​​include diethylene glycol monomethyl ether (SP value = 10.7), triethylene glycol monomethyl ether (SP value = 10.7), ethylene glycol monoisopropyl ether (SP value = 10.9), ethylene glycol monobutyl ether (SP value = 10.2), diethylene glycol monobutyl ether (SP value = 10.0), triethylene glycol monobutyl ether (SP value = 10.0), ethylene glycol monoisobutyl ether (SP value = 9.1), ethylene glycol monohexyl ether (SP value = 9.9), diethylene glycol monohexyl ether (SP value = 9.7), diethylene glycol mono-2-ethylhexyl ether (SP value = 9.3), ethylene glycol monoallyl ether (SP value = 10.8), ethylene glycol monophenyl ether (SP value = 10.8), ethylene glycol monobenzyl ether (SP value = 10.9), propylene glycol monomethyl ether (SP value = 10.0), dipropylene glycol monomethyl ether (SP value = 10.0), and dipropylene glycol monomethyl ether (SP value = 10.0). propylene glycol monomethyl ether (SP value = 9.7), tripropylene glycol monomethyl ether (SP value = 9.4), propylene glycol monopropyl ether (SP value = 9.6), dipropylene glycol monopropyl ether (SP value = 9.8), propylene glycol monobutyl ether (SP value = 9.0), dipropylene glycol monobutyl ether (SP value = 9.6), ethylene glycol monomethyl ether acetate (SP value = 10.0), ethylene glycol monoethyl ether acetate ether acetate (SP value = 9.6), ethylene glycol monobutyl ether acetate (SP value = 8.9), diethylene glycol monoethyl ether acetate (SP value = 9.4), diethylene glycol monobutyl ether acetate (SP value = 9.0), propylene glycol monomethyl ether acetate (SP value = 9.4), propylene glycol monoethyl ether acetate (SP value = 9.0), and dipropylene glycol monomethyl ether acetate (SP value = 9.2).

[0141] The organic solvents may be used in combination with a plurality of solvents, or may be used in combination with other solvents or water. For example, as described in International Publication No. 2020 / 210660, at least two solvents each having a Hansen solubility parameter δH + δP of about 16 (J / cm ３ ) 1 / 2 or less, each independently having a sum of Hansen solubility parameters δH + δP of at least about 16 (J / cm ３ ) 1 / 2, it is also possible to use developer compositions that include from about 0.25% to about 45% by volume of one or more solvents.

[0142] The concentration of the organic solvent (total when a plurality of organic solvents are mixed) in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. It is particularly preferred that the developer essentially consists of an organic solvent. The term "essentially consisting of an organic solvent" includes the case where the developer contains trace amounts of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, etc.

[0143] The water content in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably substantially no water. By keeping the water content at 10% by mass or less, good development characteristics can be obtained.

[0144] If necessary, an appropriate amount of a surfactant can be added to the developer used in the present invention. The surfactant may be the same as those described above as surfactants used in the photosensitive composition of the present invention. The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

[0145] <Development Method> Examples of development methods that can be used include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left standing for a certain period of time (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispenser nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development by replacing the solvent with another solvent may be carried out. The development time is preferably a time required for the present compound and the like in the photosensitive layer in the unexposed or exposed areas to be sufficiently dissolved, and is usually preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C. The amount of developer can be appropriately adjusted depending on the development method.

[0146] [Rinsing Step] The present pattern forming method may include, after the developing step, a step of washing with a rinse liquid containing an organic solvent.

[0147] <Rinse Liquid> The organic solvent used in the rinse liquid preferably has a vapor pressure of 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less at 20° C. By adjusting the vapor pressure of the organic solvent used in the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is improved, and further swelling due to penetration of the rinse liquid is suppressed, improving the dimensional uniformity within the wafer surface.

[0148] Various organic solvents can be used as the rinse solution. For the present compound, it is preferable to use a rinse solution containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, or water. More preferably, after development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. Even more preferably, after development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of alcohol solvents and hydrocarbon solvents. For example, as described in WO 2020 / 081483, a method can be used in which the rinse solution contains a quaternary ammonium hydroxide aqueous solution and the developer solution contains an organic solvent, or a method can be used in which the developer solution contains a quaternary ammonium hydroxide aqueous solution and the rinse solution contains an organic solvent. Specific examples of the ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent used as the rinse solution are the same as those described above for the developer. Particularly preferably, a rinse solution containing at least one organic solvent selected from the group consisting of monohydric alcohol-based solvents, hydrocarbon-based solvents, and amide-based solvents is used.

[0149] Here, examples of the monohydric alcohol solvent used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, isopropyl alcohol, cyclopentanol, and cyclohexanol, with 1-butanol, 2-butanol, 3-methyl-1-butanol, and isopropyl alcohol being preferred. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane, decane, and dodecane. Examples of the amide solvent include N,N-dimethylformamide.

[0150] The above-mentioned components may be mixed in plural, or may be mixed with an organic solvent other than those mentioned above.

[0151] The organic solvent may be mixed with water, but the water content in the rinse solution is usually 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Most preferably, the rinse solution does not contain water. By keeping the water content at 30% by mass or less, good development properties can be obtained.

[0152] The rinse solution may contain an appropriate amount of a surfactant, which may be the same as those used in the photosensitive composition described above, and the amount of surfactant used is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the rinse solution.

[0153] <Rinsing Method> In the rinsing step, the developed pattern-formed substrate is washed with a rinse solution containing the organic solvent. The washing method is not particularly limited, but examples include a method in which the rinse solution is continuously applied to a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in a tank filled with the rinse solution for a certain period of time (dipping method), and a method in which the rinse solution is sprayed onto the substrate surface (spray method). Among these, the spin coating method is preferred for washing, and after washing, the substrate is rotated at a speed of 2000 to 4000 rpm to remove the rinse solution from the substrate. The substrate rotation time can be set depending on the rotation speed within a range that achieves removal of the rinse solution from the substrate, but is typically 10 seconds to 3 minutes. Rinsing is preferably performed at room temperature. The rinse time is preferably set so that no developing solvent remains on the substrate, typically 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the rinse solution is preferably 0 to 50°C, and even more preferably 15 to 35°C. The amount of the rinse solution can be adjusted appropriately depending on the rinse method.

[0154] [Post-treatment Step] After the development treatment or rinsing treatment, a treatment can be performed using a supercritical fluid to remove the developer or rinsing solution adhering to the pattern. Furthermore, after the development treatment, rinsing treatment, or treatment with a supercritical fluid, a heat treatment can be performed to remove the solvent remaining in the pattern. The heating temperature and time are not particularly limited as long as a good resist pattern can be obtained, and are usually 40 to 160°C and 10 seconds to 3 minutes. The heat treatment may be performed multiple times.

[0155] [Uses] The photosensitive composition and the pattern forming method are suitable for use in producing semiconductor microcircuits, such as in the production of VLSIs and high-capacity microchips, and can produce substrates having patterned layers. During the production of semiconductor microcircuits, the patterned resist film is subjected to circuit formation and etching, and the remaining resist film portion is ultimately removed with a solvent or the like.

[0156] An example of the present invention will be described below. However, the present invention is not limited to this example. In the example, "parts" and "%" are by mass unless otherwise specified.

[0157] The following compounds 1 to 5 were synthesized to obtain Examples 1 to 5. The composition and ligand structure of each compound are as follows: １ Measured by H-NMR.

[0158] Synthesis Example 1: Tri-para-toluyl bismuth (hereinafter referred to as Bi(p-Tol) ３ Synthesis of Grignard solution (sometimes referred to as "Grignear solution"): Under a nitrogen atmosphere, p-toluyl bromide (43.40 g) / THF (100 mL) was added dropwise to Mg flakes (6.66 g). ３ A THF solution (150 mL) of 20.00 g of ammonium carbonate was prepared, and the Grignard solution was added dropwise to the flask. The mixture was then stirred at room temperature for 90 minutes and at 65°C for 20 minutes. 3 mL of an aqueous ammonium carbonate solution was added to the reaction mixture in an ice-water bath to quench the reaction, and further an aqueous ammonium carbonate solution and ethyl acetate were added to extract the organic layer. The organic layer was then washed with anhydrous MgSO ４The solvent was removed under reduced pressure to obtain a residue, which was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane (3:17) to obtain tri-para-toluylbismuth (29.647 g, 96.90%). 1 H-NMR(Acetone-d,ppm):7.76(m,6H),7.34(m,6H),2.31(s,9H)

[0159] Synthesis Example 2: Synthesis of 3-hydrogen-1-methyl-1,2,3,6-tetrahydrophthalene 4-Cyclohexene-1,2-dicarboxylic anhydride (9.04 g) and methanol (70 mL) were mixed in a vessel and stirred for 30 minutes at 120° C. The reaction solution was returned to room temperature, and the solvent was removed under reduced pressure to obtain 3-hydrogen-1-methyl-1,2,3,6-tetrahydrophthalene (10.792 g, 98.61%). 1 H-NMR(CDCl3,ppm):5.72(s,2H),3.74(s,3H),3.12(m,2H),2.62(m,2H),2.41(m,2H)

[0160] Synthesis Example 3 Synthesis of Compound 1 6-Methylcyclohex-3-ene-1-carboxylic acid (8.29 g), tripartuyl bismuth (14.27 g), and toluene (125 mL) were mixed and stirred at 135°C for 2 hours. Then, 3-hydrogen-1-methyl-1,2,3,6-tetrahydrophthalene (5.45 g) was added and stirred for 2 hours. The mixture was returned to room temperature, and the solvent was removed under reduced pressure to obtain the product, Compound 1 (18.33 g, 92.44%). 1 H-NMR(CDCl3,ppm):5.61(s,6H),3.66(m,3H),3.00(m,2H),2.54(m,2H),2.24(m,10H),1.91(m,2H),1.70(m,2H),1.01(d,6H)

[0161]

[0162] Synthesis Example 4 Synthesis of Compound 2 In a 100 mL recovery flask, 1.30 g of 3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (manufactured by Leap Chem) and Bi(p-Tol) ３The mixture was stirred for 4 hours at a bath temperature of 140° C. and then for 2 hours and 30 minutes at 150° C. After cooling to room temperature, the toluene was distilled off under reduced pressure and the mixture was dried to obtain 1.8 g of compound 2 as a pale yellow amorphous solid. 1 H-NMR (CDCl3) δ6.4~6.1(br.m,6H),3.7~3.5(m,9H),3.4~3.0(m,12H),1.4(m,3H),1.2(m,3H)

[0163]

[0164] Synthesis Example 5 Synthesis of 3a,5,6,7a-tetramethyl-4,7-dihydroisobenzofuran-1,3-dione 5.94 g of 2,3-dimethyl-1,3-butadiene (manufactured by Tokyo Chemical Industry Co., Ltd.), 6 mL of mesitylene (manufactured by Tokyo Chemical Industry Co., Ltd.), and 6.00 g of 2,3-dimethylmaleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 100 mL recovery flask equipped with a reflux condenser, and the mixture was stirred at 165°C to 175°C for a total of 73.5 hours. Because 2,3-dimethyl-1,3-butadiene was evaporated and lost during heating, a total of 5.1 g was added in four divided portions. After the reaction, 30 mL of ethanol was added, the mixture was left to stand overnight, and the precipitated solid was collected by filtration, washed with 5 mL of hexane, and dried, yielding 7.0 g of a brown solid. This was confirmed to be the desired 3a,5,6,7a-tetramethyl-4,7-dihydroisobenzofuran-1,3-dione by GC-MS analysis. 1 H-NMR (CDCl3) δ2.45(d,J=15Hz,2H),2.07(br.d,J=15Hz,2H),1.72~1.68(m,6H),1.33(s,6H)

[0165] Synthesis Example 6 Synthesis of 6-methoxycarbonyl-1,3,4,6-tetramethyl-cyclohex-3-ene-1-carboxylic acid 6.97 g of 3a,5,6,7a-tetramethyl-4,7-dihydroisobenzofuran-1,3-dione was added to 110 mL of methanol and 6.92 g of sodium methoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature to dissolve, followed by stirring for 40 minutes at 120° C. After cooling to room temperature, 100 mL of 1N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) and 50 mL of dichloromethane were added for separation and washing, the oil phase was dried over magnesium sulfate, filtered through a short column packed with silica gel, and the dichloromethane was removed under reduced pressure, yielding 6.4 g of the target 6-methoxycarbonyl-1,3,4,6-tetramethyl-cyclohex-3-ene-1-carboxylic acid. 1 H-NMR (CDCl3) δ3.68 (s, 3H), 2.58 (br.t, J=17Hz, 2H), 2.0 to 1.9 (m, 2H), 1.62 (br.s, 6H), 1.35 (s, 3H), 1.33 (s, 3H)

[0166] Synthesis Example 7 Synthesis of Compound 3 In a 100 mL recovery flask, 1.05 g of 6-methoxycarbonyl-1,3,4,6-tetramethyl-cyclohex-3-ene-1-carboxylic acid, Bi(p-Tol), ３ The mixture was stirred for 2 hours at a bath temperature of 75° C. and then for 4 hours at 100° C. After cooling to room temperature, the tetrahydrofuran was distilled off under reduced pressure and the mixture was dried to obtain 1.0 g of compound 3 as a light brown amorphous solid. 1 H-NMR (CDCl3) δ3.58 (s, 3H), 2.48 (br.t, J=19Hz, 2H), 1.95 to 1.85 (m, 2H), 1.6 to 1.4 (br.m, 6H), 1.3 to 1.1 (m, 6H).

[0167]

[0168] Synthesis Example 8 Synthesis of Compound 4 Under a nitrogen atmosphere, 2.83 g (5.9 mmol) of tris-para-toluylbismuth, 2.47 g (17.6 mmol) of 6-methyl-3-cyclohexene-1-carboxylic acid, and 35 ml of dehydrated toluene were placed in a reaction vessel and heated with stirring at 140°C for 5 hours. After that, the mixture was cooled to room temperature, and the solvent was concentrated under reduced pressure to obtain a white powder (3.51 g) as a residue. NMR analysis of the obtained solid confirmed that it was Compound 4 shown below. 1 H-NMR (CDCl 3, ppm): 5.5(m,2H), 2.2(m, 4H), 1.9(m, 1H), 1.7(m, 1H), 1.0(d,3H)

[0169]

[0170] Synthesis Example 9 Synthesis of Compound 5 In a nitrogen atmosphere, 1.5 g (3.11 mmol) of tris-para-tolylbismuth, 1.44 g (9.35 mmol) of 1,6-dimethyl-3-cyclohexene-1-carboxylic acid, and 7.5 ml of dehydrated toluene were placed in a reaction vessel and heated with stirring at 100°C for 4 hours. After that, the mixture was cooled to room temperature, and the solvent was concentrated under reduced pressure to obtain a white powder (2.08 g) as a residue. NMR analysis of the obtained solid confirmed that it was Compound 5 shown below. 1 H-NMR (CDCl 3, ppm):5.6(m, 2H), 2.5(d, 2H), 2.3(d, 2H), 2.0(m, 1H), 1.9(m, 3H), 1.0(m, 3H)

[0171]

[0172] Examples 1 to 5 Preparation of Photosensitive Compositions (Resist Solutions) The compounds 1 and 2 were each dissolved in ethyl lactate, the compound 3 in 2-heptanone, and the compounds 4 and 5 in cyclohexanone to a concentration of 5% by mass, and the resulting solution was filtered through a 0.2 μm filter to obtain resist solutions.

[0173] The prepared resist solution was applied by spin coating onto a patterned substrate (silicon wafer) to form a resist film with a thickness of about 40 nm. The obtained resist film was baked for 90 seconds at 90°C for Compounds 1 and 2, at 130°C for Compound 3, at 90°C for Compound 4, and at 120°C for Compound 5, and then patterned using an electron beam lithography system (electron beam acceleration voltage: 100 keV).

[0174] <Development> After pattern writing, compounds 1 and 2 were developed with ethyl lactate (25°C, 60 seconds), compound 3 was developed with 4-methyl-2-pentanol (25°C, 60 seconds), compound 4 was developed with a mixed solution of propylene glycol and propylene glycol monomethyl ether acetate in a ratio of 7:3 (25°C, 30 seconds), and compound 5 was developed with propylene glycol monomethyl ether acetate (25°C, 30 seconds) to obtain negative patterns, which were designated as Examples 1 to 5, respectively.

[0175] <Resolution Evaluation> Resolution evaluation was performed using an electron beam lithography device. Line and space (line:space = 1:1) patterns with hp (half pitch) of 100 nm, 50 nm, 30 nm, and 20 nm were drawn, developed, and each pattern was observed under a scanning electron microscope to evaluate the drawn patterns. A rating of "A" was given when a line and space pattern was confirmed, a rating of "B" was given when a pattern was confirmed but partially crosslinked, and a rating of "C" was given when no pattern was confirmed. The results are shown in Table 1.

[0176] Comparative Example 1 Polystyrene (PS, weight average molecular weight 4000) manufactured by Aldrich was dissolved in propylene glycol monomethyl ether acetate at a concentration of 2% by mass and filtered through a 0.2 μm filter to prepare a resist solution. After pattern writing, the PS was developed with propylene glycol monomethyl ether acetate (25°C, 60 seconds) to obtain a negative pattern, which was designated Comparative Example 1. The resist solution of Comparative Example 1 was evaluated in the same manner as in the Examples. The results are shown in Table 1.

[0177]

[0178] <Measurement of Sensitivity> Extreme ultraviolet (EUV) exposure was carried out with varying doses in Examples 1, 3, 4, and 5 and Comparative Example 1, and the film thickness of the developed pattern was measured with a contact step gauge. The EUV dose at which the amount of change in film thickness was maximized was determined as an index of sensitivity. The sensitivity was measured using the exposure dose (unit: mJ / cm ２ The results are shown in Table 2.

[0179]

[0180] From the results in Table 2, it was confirmed that, compared with Comparative Example 1, Examples 1, 3, 4 and 5 had a smaller EUV irradiation dose when the amount of change in film thickness was at its maximum, and therefore had higher sensitivity.

[0181] [Results] From the results of the electron beam (EB) writing test, it was possible to form half-pitch (hp) 100 nm, 50 nm line and space (L&S) patterns (1:1) in Examples 1 to 5, and in particular, it was possible to form hp 20 mm line and space (L&S) patterns (1:1) in Examples 1, 4, and 5. Furthermore, as shown in Table 2, it was also confirmed that the samples had very high sensitivity to EUV exposure.

[0182] <Evaluation of Resist Solution Stability> The resist solutions of Compounds 1 to 5 prepared in the preparation of photosensitive compositions (resist solutions) were left at room temperature to conduct a stability test for the resist solutions. The results are shown in Table 3. The resist solutions of Compounds 1 to 5 showed no precipitates even after being left at room temperature for two weeks. Therefore, it was found that Compounds 1 to 5 according to the present invention have high resist solution stability.

[0183]

[0184] From the above results, it is possible to determine whether a compound containing a metal atom and a carboxylate ligand A having a cyclic structure, in which the carboxylate ligand A has a cyclic structure that bonds to a carboxylate group, and in which a carbon C in the cyclic structure that bonds to the carboxylate group is a １ is a tertiary or quaternary carbon, and carbon C １ The carbon C adjacent to ２is the substituent R １ and the substituent R １ Compounds in which is an organic group or a halogen atom have high sensitivity to EUV, high resolution, and the resist solution is stable and can be stored for a long period of time, and are highly practical as photoresists capable of forming ultrafine patterns.

Claims

1. A compound containing a metal atom and a carboxylate ligand A having a cyclic structure, wherein the carboxylate ligand A has a cyclic structure bonded to a carboxylate group, and the carbon C in the cyclic structure bonded to the carboxylate group is １ is a tertiary or quaternary carbon, and carbon C in the cyclic structure １ The carbon C adjacent to ２ is a substituent R １ wherein the substituent R １ is an organic group or a halogen atom.

2. The compound of claim 1, wherein the cyclic structure contains a double bond.

3. The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (1): In the general formula (1), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 1 to 8, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 8, and ｎ is the substituent R ２ and has a substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is an integer of 0 to 2n.

4. The substituent R in the general formula (1) １ is a hydrocarbon group or an ester group.

5. The compound according to claim 3, wherein m in the general formula (1) is 0.

6. The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (5): In the general formula (5), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and has a substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m represents the number of the cyclic structure and the number of the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

7. The substituent R in the general formula (5) １ is a hydrocarbon group or an ester group.

8. The compound according to claim 6, wherein m in the general formula (5) is 0.

9. The compound of claim 1, wherein the metal atom is a poor metal atom.

10. The compound according to claim 9, wherein the poor metal atom is at least one selected from the group consisting of bismuth and antimony.

11. The compound according to claim 1, wherein the cyclic structure of the carboxylate ligand A is a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, or a norbornane ring.

12. The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (2): In formula (2), the substituent R ３ is any one of an alkyl group, a saturated alicyclic group, an unsaturated alicyclic group, and an aromatic group, and the substituent R ３ wherein hydrogen may be substituted by halogen; and l represents the coordination number and is an integer of 1 to 3.

13. The compound according to claim 1, wherein the compound containing the metal atom and the carboxylate ligand A having a cyclic structure is represented by the following general formula (3): In the general formula (3), M is the metal atom, and the substituent R ３ and substituent R ４ are alkyl groups, saturated alicyclic groups, unsaturated alicyclic groups, or aromatic groups, and may be the same or different; ３ and substituent R ４ The structure of the compound (I) may contain an unsaturated hydrocarbon or a halogen atom. x is an integer of 1 to 3.

14. The substituent R in the general formula (3) ３ is a methyl group, and the substituent R ４ is a methylcyclohexenyl group.

15. The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (6): In the general formula (6), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and the carbon C １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ and substituent R １ａ are each independently an organic group or a halogen atom, ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are each independently an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituent R １ or the substituent R １ａ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and the substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m represents the number of the cyclic structure and the number of the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

16. The substituent R in the general formula (6) １ or a substituent R １ａ and each independently represent a hydrocarbon group or an ester group.

17. The compound according to claim 1, wherein the carboxylate ligand A is a ligand represented by the following general formula (7): In the general formula (7), the carbon C to which the carboxylate group is bonded １ Substituent R １ａ and the carbon C １ and the adjacent carbon C ２ The substituent R １ and substituent R １ｂ and the substituent R １ , the substituent R １ａ or the substituent R １ｂ are each independently an organic group or a halogen atom, ｎ is either a carbon atom or a heteroatom, or may not exist as an atom and form a single bond, and C １ ,C ２ , C ３ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 0 to 7, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ , substituent R １ａ or substituent R １ｂ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and has a substituent R ２ When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m represents the number of the cyclic structure and the number of the substituent R ２ is an integer of 0 to 2n when they are connected by a single bond.

18. The substituent R in the general formula (7) １ , substituent R １ａ or a substituent R １ｂ and each independently represent a hydrocarbon group or an ester group.

19. A cluster compound in which the compound according to claim 1 is a compound having a plurality of the metal atoms, and the metal atoms are bonded to each other via a metal-metal bond or one to three atoms.

20. The cluster compound according to claim 19, comprising the metal atom and the carboxylate ligand A represented by the following general formula (4): In the general formula (4), the carbon C to which the carboxylate group is bonded １ and the adjacent carbon C ２ The substituent R １ and the substituent R １ is an organic group or a halogen atom, and A ｎ is a carbon or heteroatom, C １ ,C ２ ,A ｎ constitutes a 3- to 10-membered ring structure, n is an integer of 1 to 8, and in the ring structure, A ｎ is a substituent R ２ and the substituent R ２ are an organic group or a halogen atom when m is 1, and are each independently an organic group or a halogen atom when m is 2 or more, and the substituents R １ may be the same as or different from each other. n is an integer of 2 to 7, and ｎ is the substituent R ２ and the substituent R ２ When is an alkylene group, it may be a polycyclic structure in which alkylene groups are crosslinked, and m is an integer of 0 to 2n. 1 represents the coordination number and is an integer of 1 to 3, and when it is 2 or more, the structures of the general formula (4) may be the same or different.

21. The cluster compound of claim 20, wherein the metal atom is a poor metal atom.

22. The cluster compound according to claim 21, wherein the poor metal atom is at least one selected from the group consisting of bismuth and antimony.

23. A method for producing the compound according to any one of claims 1 to 18, comprising reacting a compound containing a metal atom with a carboxylic acid having a carboxylate ligand A structure in a solution.

24. A photosensitive composition comprising at least one compound selected from the compounds according to any one of claims 1 to 18 and the cluster compounds according to any one of claims 19 to 22.

25. The photosensitive composition of claim 24, further comprising a solvent.

26. A photosensitive composition comprising at least one compound selected from the group consisting of the compound described in any one of claims 1 to 18 and the cluster compound described in any one of claims 19 to 22, in a concentration of 50 to 100 mass percent of the total solids.

27. The photosensitive composition according to claim 24, which reacts with actinic radiation having a wavelength of 6 nm or more and 15 nm or less.

28. A method for forming a pattern, comprising the steps of applying the photosensitive composition of claim 24 to a substrate, exposing it to actinic radiation, and developing it.

29. The pattern formation method according to claim 28, wherein the development is carried out using a developer, and the developer is an organic solvent having a solubility parameter (SP value) of 7.5 or more and 11 or less.

30. A substrate having a patterned layer obtained by the patterning method according to claim 28.

31. A method for manufacturing a substrate, in which a pattern layer is formed by the pattern forming method according to claim 28.

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