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

Abstract

To provide a compound capable of obtaining a photosensitive composition having high practicality as a photoresist capable of forming an ultrafine pattern.SOLUTION: The compound of the present invention is a compound containing a metallic atom and a carboxylate ligand A having a cyclic structure, wherein the carboxylate ligand A has a cyclic structure bonded to a carboxylate group, a carbon atom C1 in the cyclic structure bonded to the carboxylate group in the cyclic structure is a third or fourth carbon atom, a carbon atom C1 adjacent to the carbon atom C2 in the cyclic structure has a substitutional group R1, and the substitutional group R1 is an organic group or a halogen atom.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound or cluster compound that is suitable for use in ultra-microlithography processes such as those used in the manufacture of ultra-LSIs and high-capacity microchips, as well as 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. [Background technology]

[0002] 2. Description of the Related Art In the manufacturing process of semiconductor devices, fine processing is carried out by lithography using a photoresist composition. In semiconductor photolithography, circuit patterns become smaller as semiconductor devices become smaller in accordance with Moore's Law, and further miniaturization is desired. The development of photolithography can be broadly divided into the shift to shorter wavelength light sources for exposure equipment and the accompanying development of new photoresists. Photoresists are required to meet all of the requirements of high resolution, low roughness, and high sensitivity. Conventional resists are photosensitive compositions containing a photoacid generator based on an organic polymer, and are called chemically amplified resists. This type of resist promotes a chemical reaction accompanied by the diffusion of acid, but the acid diffusion process can cause line edge roughness (LER), which can result in a decrease in resolution, making it considered incompatible with ultra-fine patterns.

[0003] In recent years, non-chemically amplified photoresists (hereafter 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 also functions as the base material. As no acid diffusion is involved, line edge roughness can be improved, and so they are expected to be 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 listed below disclose methods for forming resist patterns using extreme ultraviolet light (EUV light), electron beams, or the like. In addition, Non-Patent Documents 4 and 5 disclose a compound obtained by mixing Zr(OBu)4 and endo-5-Norbornene-2-carboxylic acid [Zr6O4(OH)4(OOC-Norb) 12 However, there is no disclosure that the ligand of the obtained compound has a predetermined substituent at carbon C2 adjacent to carbon C1 in the ring structure that bonds to the carboxylate group, or that the compound can be used as a metal-containing resist. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-108781 [Patent Document 2] Japanese Patent Application Laid-Open No. 2001-072716 [Patent Document 3] Japanese Patent Application Publication No. 2017-173537 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-185484 [Patent Document 5] Patent Publication No. 2021-102604 [Patent Document 6] International Publication No. 2024 / 143204 [Non-patent literature]

[0006] [Non-Patent Document 1] Minoru Toriumi etc.,Proc.SPIE,9779(2016)97790G [Non-patent document 2] Lianjia Wu etc.,Proc.SPIE,10957(2019)109570B [Non-patent document 3] Neha Thakur etc.,Proc.SPIE,10957(2019)10957D [Non-patent document 4] Coord.Chem.Rev.,2021,438,Articles No.213886,Pages 1-70 [Non-Patent Document 5] J.Mater.Chem.,16(2006)5537-5539 Summary of the Invention [Problem to be solved by the invention]

[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 a compound having a specific structure is suitable as a photoresist suitable for ultrafine patterns. Therefore, an object of the present invention is to provide a compound or cluster compound suitable for a photosensitive composition that can realize finer circuit patterns, a photosensitive composition containing the compound or cluster compound, a pattern forming method using the photosensitive composition, a substrate having a pattern layer obtained by the pattern forming method, and a method for manufacturing the substrate. [Means for solving the problem]

[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 the carbon C1 in the cyclic structure bonded to the carboxylate group is a tertiary or quaternary carbon, and the carbon C2 adjacent to the carbon C1 in the cyclic structure is a substituent R 1 and the substituent R 1is 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] TIFF2026009009000001.tif43161 In the general formula (1), the carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is bonded is bonded to 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, C1, C2, 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 the 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 a plurality of A n is the substituent R 2 and having 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 general formula (5), the carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is bonded has 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, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, 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 the 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 a plurality of A n is the substituent R 2 and having a substituent R 2 When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is 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 a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, or 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] TIFF2026009009000003.tif46170In 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, and l represents the coordination number and is an integer of 1 to 3.

[0025]

[13] The compound according to [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] TIFF2026009009000004.tif46170In 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 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 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] TIFF2026009009000005.tif47161In general formula (6), a substituent R is attached to the carbon atom C1 to which the carboxylate group is bonded. 1a and the carbon C2 adjacent to the carbon C1 has the substituent R 1 and the substituent R 1 and substituent R 1a are each independently an organic group or a halogen atom, and A n is either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, 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 the 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 a plurality of A 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 is 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 and each independently represent 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] TIFF2026009009000006.tif52161In general formula (7), a substituent R is attached to the carbon atom C1 to which the carboxylate group is bonded. 1aand the carbon C2 adjacent to the carbon C1 has 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, and A n is either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, 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 the 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 a plurality of A n is the substituent R 2 and having a substituent R 2 When is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure, and m is 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 and each independently represent a hydrocarbon group or an ester group.

[0034]

[19] . A cluster compound according to [1], which has a plurality of the metal atoms, wherein the plurality of 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 general formula (4), the carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is bonded has 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, C1, C2, 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 the 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 a plurality of A 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 is an integer of 0 to 2n. 1 represents the coordination number, and is an integer of 1 to 3. 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 a 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 described in any one of [1] to

[18] and the cluster compounds described in any one of

[19] to

[22] , in a mass percent concentration of 50 to 100 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 forming 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 formation method according to

[28] or

[29] . [Effects of the Invention]

[0048] The compound of the present invention is suitable as a photosensitive composition, is relatively easy to synthesize, and is suitable for mass production. In addition, it has high sensitivity to extreme ultraviolet (EUV) light, high throughput, and high resolution, and is 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 a long period of time. On the other hand, the bond between the carboxylate group and the cyclic structure is also easily cleaved by actinic radiation such as electron beam (EB) irradiation or extreme ultraviolet (EUV) exposure, and it is presumed that this cleavage causes insolubilization in organic solvents, resulting 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 places where the expression "~" is used 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 that forms 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 the carboxylate group, and the carbon C1 in the cyclic structure that bonds to the carboxylate group is a tertiary or quaternary carbon, and the carbon C2 adjacent to the carbon C1 in the cyclic structure is a substituent R 1 It has. 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 compound of the present invention refers to a metal complex molecule having a metal atom and a ligand, in which one or more metal atoms are bound to each other directly or through a bridging ligand, and includes a mononuclear complex or a polynuclear complex, and may be in the form of either a complex compound or a cluster compound. The compound may contain oxygen and / or a hydroxyl group in 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 hydroxyl group is coordinated to a metal. The cluster compound referred to here means a compound having multiple metal atoms, in which the metal atoms have metal-metal bonds or are bonded to each other via 1 to 3 atoms. Furthermore, a carboxylate ligand is a ligand having at least one carboxylate group, and a carboxylate group is a functional group having a chemical structure of -C(=O)O-.

[0053] The compounds contain metal atoms, which may be transition metal atoms or poor metal atoms. 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 that have 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, 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 compound comprises a carboxylate ligand A, which 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 less susceptible to hydrolysis by moisture or oxygen, resulting in stability that is less susceptible to deterioration even when stored for a long period of time. 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, the carbon C1 to which the carboxylate group is bonded is a tertiary or quaternary carbon, and the carbon C2 adjacent to the carbon C1 in the cyclic structure is bonded to a substituent R 1 It has the following characteristics.

[0057] Substituent R 1 is, but is not limited to, 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. Substituent R 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, halogenated ethyl, 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, ethyl ester, and n-propyl ester groups, and aromatic ester groups such as phenyl ester groups. Examples of the sulfonyl group include methylsulfonyl, ethylsulfonyl, and n-propylsulfonyl groups. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, and phenoxy groups. Examples of amino groups include amino alkyl groups such as amino (-NH), aminomethyl (NH-CH-), aminoethyl (NH-C-H-), and aminopropyl (NH-C-H-), as well as dialkylamino groups such as dimethylamino ((CH)N-) and diethylamino ((C-H)N-). Examples of amide groups include alkylamide groups such as methylamide ((CH)N(C=O)-) and ethylamide ((C-H)N(C=O)-). Examples of carbonyl oxygen groups (>C=O) include halogen atoms such as fluorine, chlorine, and bromine. The above substituent R 1 In the specific example, the structure may contain an unsaturated hydrocarbon or a halogen atom. In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R 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] TIFF2026009009000008.tif43161

[0061] In the general formula (1), a substituent R is attached to the carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is attached. 1 and having a substituent R 1 is an organic group or a halogen atom. A n is a carbon or heteroatom, C1, C2, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 1 to 8. In the cyclic structure, A n is the 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 substituent R 1 may be the same as or different from. n is an integer of 2 to 8, and a plurality of A n is the substituent R 2 and having a substituent R 2 When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. 2 When are connected by a single bond, m is an integer of 0 to 2n.

[0062] In the above general formula (1), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group is attached. 1 In this case, carbon C1 is a tertiary carbon. Substituent R 1 is an organic group or a halogen atom, and the substituent R 1 The hydrogen atoms in the structure may be substituted with halogen atoms such as fluorine, chlorine, and bromine. Substituent R 1 Specific examples of the substituent R include those mentioned above. 1 The substituent R 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.

[0063] In the above general formula (1), A n is either a carbon or heteroatom. C1, C2, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 1 to 8. In the cyclic structure, A n is the substituent R 2 may have A n Heteroatoms in C1, C2, A include oxygen, nitrogen, phosphorus, sulfur, silicon, etc. n The 3- to 10-membered cyclic structure may be a saturated cyclic structure or an unsaturated cyclic structure. An unsaturated cyclic structure is preferred, and A n It is preferred that the moiety represented by the formula (I) has an unsaturated bond. In addition, 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 substituent R 1 may be the same as or different from. 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 may be the same as or different from. n is an integer of 2 to 8, and a plurality of A n is the substituent R 2 and having 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. Substituent R 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 preventing water molecules from approaching from the outside. This makes it less susceptible to hydrolysis and provides excellent long-term stability. 1 is an alkyl group, the substituent R 2 is an alkylene group, the substituent R 1 and the substituent R 2 It is preferred that the rings do not form a bridged polycyclic structure. In addition, from the viewpoints of solubility in a coating solvent and a developer and molecular size, n in the general formula (1) is preferably 1 to 7, more preferably 2 to 5. Similarly to n, in the general formula (1), from the viewpoints of solubility in a coating solvent and a developer and molecular size, m is 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 preferable for ease of production. TIFF2026009009000009.tif45161

[0065] In the general formula (5), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group A is attached. 1 and having a substituent R 1 is an organic group or a halogen atom. A n is either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, 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 the substituent R 2 and may have a substituent R 2are 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 may be the same as or different from. n is an integer from 2 to 7, and a plurality of A n is the substituent R 2 and having 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] In the above general formula (5), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group is attached. 1 In this case, carbon C1 is a tertiary carbon. The other carbon C3 adjacent to carbon C1 does not have a substituent. Substituent R 1 is either an organic group or a halogen atom, and the substituent R 1 The hydrogen atoms in the structure may be substituted with halogen atoms such as fluorine, chlorine, and bromine. 1 Specific examples of the substituent R 1 The substituent R 1 The substituent R 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, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. In the cyclic structure, A n is the substituent R 2 may have An Heteroatoms in C1, C2, A include oxygen, nitrogen, phosphorus, sulfur, silicon, etc. n The 3- to 10-membered cyclic structure may be a saturated cyclic structure or an unsaturated cyclic structure. An unsaturated cyclic structure is preferred, and A is more preferred. n It is preferred that the moiety represented by the formula (I) has an unsaturated bond. Substituent R 2 are each independently an organic group or a halogen atom, and the substituent R 1 may be the same as or different from. 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 having 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. Substituent R 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 preventing water molecules from approaching from the outside. This makes it less susceptible to hydrolysis and provides excellent long-term stability. 1 is an alkyl group, the substituent R 2 is an alkylene group, the substituent R 1 and the substituent R 2 It is preferred that the rings do not form a bridged polycyclic structure. Furthermore, in terms of the solubility in the coating solvent and the developer and the molecular size, n in the general formula (5) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, in terms of the solubility in the coating solvent and the developer and the molecular size, m in the 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] TIFF2026009009000010.tif47161

[0070] In the general formula (6), a substituent R is attached to the carbon atom C1 to which the carboxylate group is bonded. 1a and the carbon C2 adjacent to the carbon C1 has a substituent R 1 and having a substituent R 1 or a substituent R 1a are each independently an organic group or a halogen atom. A n is either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. In the cyclic structure, A n is the substituent R 2 may have n is an integer of 2 to 7, and a plurality of A n is the substituent R 2 and having 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] In the above general formula (6), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group is attached. 1Carbon C1 is a quaternary carbon, and the substituent R 1a In addition, the other carbon atom C3 adjacent to carbon C1 has no substituent. Substituent R 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 may be substituted with halogen atoms such as fluorine, chlorine, and bromine. Substituent R 1 or a substituent R 1a Specific examples of the substituent R 1 The substituent R 1 The substituent R 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. Substituent R 1a is an electron donating group, and the bond between C1 and the carbonyl carbon adjacent thereto is easily cleaved by exposure, thereby increasing the exposure sensitivity. Therefore, a hydrocarbon group is preferred. 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, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. A n Heteroatoms include oxygen, nitrogen, phosphorus, sulfur, silicon, etc. n The 3- to 10-membered ring structure may be a saturated ring structure or an unsaturated ring structure. Also, C1, C2, C3, A n In the ring structure of n is the substituent R2 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 substituent R 1 or a substituent R 1a may be the same as or different from. 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 having 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 they are connected by a single bond, it is an integer of 0 to 2n. Substituent R 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 preventing water molecules from approaching from the outside. This makes it less susceptible to hydrolysis and provides 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 the substituent R 1a or a substituent R 2 It is preferred that the rings do not form a bridged polycyclic structure. In addition, from the viewpoint of solubility in a coating solvent and a developer and molecular size, n in the general formula (6) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoint of solubility in a coating solvent and a developer and molecular size, m in the 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] TIFF2026009009000011.tif52161

[0075] In the general formula (7), a substituent R is attached to the carbon atom C1 to which the carboxylate group is bonded. 1a and the carbon C2 adjacent to the carbon C1 has a 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. A n is either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. In the cyclic structure, A n is the substituent R 2 may have n is an integer from 2 to 7, and a plurality of A n is the substituent R 2 and having 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] In the above general formula (7), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group is attached. 1 and substituent R 1b Carbon C1 is a quaternary carbon, and the substituent R 1a In addition, the other carbon atom C3 adjacent to carbon C1 has no substituent. Substituent R 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 may be substituted with halogen atoms such as fluorine, chlorine, and bromine. Substituent R 1 , substituent R 1a or a substituent R 1b Specific examples of the substituent R 1 The same can be mentioned. Substituent R 1 The substituent R 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. Substituent R 1a is an electron donating group, and the bond between C1 and the carbonyl carbon adjacent thereto is easily cleaved by exposure, thereby increasing the exposure sensitivity. Therefore, a hydrocarbon group is preferred. 1a The number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Substituent R 1b is preferably a hydrocarbon group in terms of molecular size and the ability to block the approach of water molecules to prevent unwanted 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, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. In the cyclic structure, A n is the substituent R 2 may have A n Heteroatoms include oxygen, nitrogen, phosphorus, sulfur, silicon, etc. n The 3- to 10-membered cyclic structure may be a saturated cyclic structure or an unsaturated cyclic structure. An unsaturated cyclic structure is preferred, and A n It is preferred that the moiety represented by the formula (I) has an unsaturated bond. Also, C1, C2, C3, A n In the ring structure of n is the 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 substituent R 1 , substituent R 1a or a substituent R 1b may be the same as or different from. 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 having 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. These substituents R 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 preventing water molecules from approaching from the outside. This makes it less susceptible to hydrolysis and provides 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 the substituent R 1a , substituent R 1b or a substituent R 2 It is preferred that the rings do not form a bridged polycyclic structure. In addition, from the viewpoint of solubility in a coating solvent and a developer and molecular size, n in the general formula (7) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, from the viewpoint of solubility in a coating solvent and a developer and molecular size, m in the 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] TIFF2026009009000012.tif48161

[0080] In the general formula (8), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group A is attached. 1 and the carbon C3 adjacent to the carbon C1 has a substituent R 1c and having a substituent R 1 or a substituent R 1c are each independently an organic group or a halogen atom. A nis either a carbon atom, a heteroatom, or may not exist as an atom and form a single bond, and C1, C2, C3, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 0 to 7. In the cyclic structure, A n is the substituent R 2 may have n is an integer of 2 to 7, and a plurality of A n is the substituent R 2 and having 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] In the above general formula (8), a substituent R is attached to the carbon C2 adjacent to the carbon C1 to which the carboxylate group A is attached. 1 The carbon C1 is a tertiary carbon. The other carbon C3 adjacent to the carbon C1 is a substituent R 1c It has. 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 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 The substituent R 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. Substituent R 1c is preferably a hydrocarbon group in terms of molecular size and the ability to block the approach of water molecules to prevent unwanted 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 Heteroatoms include oxygen, nitrogen, phosphorus, sulfur, silicon, etc. n The 3- to 10-membered cyclic structure may be a saturated cyclic structure or an unsaturated cyclic structure. An unsaturated cyclic structure is preferred, and A n It is preferred that the moiety represented by the formula (I) has an unsaturated bond. 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 substituent R 1 or a substituent R 1c may be the same as or different from. 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 a plurality of A n is the substituent R 2 and having a substituent R 2 When m is an alkylene group, the alkylene groups may be crosslinked to form a polycyclic structure. 2 is an integer of 0 to 2n when they are connected by a single bond. These substituents R 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 preventing water molecules from approaching from the outside. This makes it less susceptible to hydrolysis and provides 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 the substituent R 2 or a substituent R 1c It is preferred that the rings do not form a bridged polycyclic structure. In addition, from the viewpoint of solubility in a coating solvent and a developer and molecular size, n in the general formula (8) is preferably 0 to 7, more preferably 1 to 4. Similarly to n, in the general formula (8), from the viewpoint of solubility in a coating solvent and a developer and molecular size, m is 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 preferable in terms of ease of production and development speed in a developer.

[0084] TIFF2026009009000013.tif46170

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

[0086] Substituent R 3Examples 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. 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. The substituent R 3 The number of carbon atoms in the substituent R is preferably 1 to 10, more preferably 1 to 5. 3 is 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 techniques, for example, by NMR. In addition, in this 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 this 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] TIFF2026009009000014.tif46170

[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 R4 The structure may contain unsaturated hydrocarbons or halogen atoms. x is an integer of 1 to 3.

[0091] Substituent R 4 In 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. The substituent R 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. Substituent R 4 is a saturated alicyclic group or an unsaturated alicyclic group, the substituent R 4 The carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is bonded has a 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] TIFF2026009009000015.tif52161

[0095] In the general formula (4), the carbon atom C2 adjacent to the carbon atom C1 to which the carboxylate group is bonded has a substituent R 1 and having a substituent R 1 is an organic group or a halogen atom. A n is a carbon or heteroatom, C1, C2, A n constitutes a cyclic structure of 3 to 10 members, and n is an integer of 1 to 8. In the cyclic structure, A n is the 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 substituent R 1 may be the same as or different from. Substituent R 1 or a substituent R 2 is the substituent R 1 or a substituent R 2 The same can be mentioned. n is an integer of 2 to 8, and a plurality of A n is the substituent R 2 and having 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. In the general formula (4), m is preferably 0 to 5, more preferably 0 to 1, and particularly preferably 0, from the viewpoint of solubility in a coating solvent and a developer and molecular size, similar to n. When m=0, the substituent R 2 Therefore, the system will not have the following characteristics. 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 the present compound is preferably 100 to 8,000, more preferably 200 to 8,000, and particularly preferably 300 to 7,000. When the present compound is in the form of a mononuclear complex, the molecular weight is preferably 100-1,000, more preferably 200-800, and particularly preferably 300-700. When the present 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 upper limit, the volume is small, and roughness and resolution are expected to be high. On the other hand, if the molecular weight is above the lower limit, the coating properties and etching resistance tend to be improved. Note that this molecular weight is a guideline, and lithography properties are not determined by it alone, so it is not limited to this. The molecular weight of the present compound can be analyzed by known methods, for example, by NMR.

[0097] [Manufacturing method] This compound can be produced, for example, by reacting a compound containing a metal atom with a carboxylic acid having the structure of a carboxylate ligand A. For example, they can be produced by reacting a solution containing a compound containing a metal atom with a carboxylic acid having a structure of carboxylate ligand A. Furthermore, when synthesizing a compound having a non-metallic metal atom and two different carboxylate ligands A, for example, they can be produced by reacting a solution containing a compound containing a non-metallic metal atom described below with a carboxylic acid having a structure of carboxylate ligand A1 and a carboxylic acid having a structure of carboxylate ligand A2 that has a structure different from that of carboxylate ligand A1.

[0098] When the compound containing a metal atom is a compound containing a transition metal atom, examples of the metal atom include zirconium, hafnium, and 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. In the case of a compound containing a poor metal atom, examples of the metal atom include bismuth and antimony, and examples of this compound include organic compounds containing poor metals, specifically trisphenylbismuth, tris-paratoluylbismuth, trisphenylantimony, tris-paratoluylantimony, etc.

[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 in the following chemical formula (5) has a saturated alicyclic structure composed of six carbon atoms, and the carbon in the saturated alicyclic structure that bonds to the carboxylic acid of the carboxylate group is tertiary, with an ethyl ester group on one of the carbons adjacent to the tertiary carbon.

[0100] TIFF2026009009000016.tif38170

[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 propylsulfonic acid ester cyclohexane-1-carboxylic acid, 2-(N-methylamido)cyclohexane-1-carboxylic acid, 2-fluorocyclohexyl 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 estercyclohex-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 filtering it. The solution after the reaction may be cooled to -30°C to 20°C in order to obtain the precipitate or crystallize the product. If no precipitation of the product is observed after the reaction, the target product can be recovered by distilling off the solvent by applying a 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 if the volume is small, a Schlenk tube or the like can be used. The reaction is preferably carried out under a nitrogen or argon atmosphere. The reaction vessel is preferably a flask equipped with a reflux condenser, and when heating, the reaction is preferably carried out in a nitrogen or argon atmosphere.

[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 substance amount ratio of 1:1 to 1:3, more preferably 1:3. Furthermore, when synthesizing a compound having a poor metal atom and two different carboxylate ligands A, if the compound obtained in the above process is a compound having a 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 a compound containing a carboxylate ligand A1 and a poor metal atom and a 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.

[0106] The present photosensitive composition contains the present compound at a mass percent concentration of 50 to 100, preferably 60 to 100, and particularly preferably 70 to 90, of total solids relative to the total of all components of the photosensitive composition other than the solvent. The term "total solids" refers to solids obtained by evaporating the photosensitive composition to dryness by evaporation or the like. The concentration of the present compound in the present photosensitive composition is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 50% by mass or less, and particularly preferably 1% by mass or more and 40% by mass or less. When the concentration of the present compound in the present photosensitive composition is equal to or higher than the above 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 upon 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 upon exposure 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, upon exposure to actinic radiation.

[0109] The photoacid generators can be used singly or in combination of two or more. When two or more types are used in combination, for example, (1) two types of photoacid generators with different acid strengths are used in combination, or (2) two types of photoacid generators with different sizes (molecular weight or number of carbon atoms) of the acid generated are used in combination, etc. are preferred. Examples of the embodiment (1) include a combination of a fluorine-containing sulfonic acid generator and a tris(fluoroalkylsulfonyl)methide acid generator, a combination of a fluorine-containing sulfonic acid generator and a fluorine-free sulfonic acid generator, and a combination of an alkylsulfonic acid generator and an arylsulfonic acid generator. As an example of the embodiment (2), it is possible to use two kinds of acid generators in combination, each of which generates an acid anion with a difference of four or more carbon atoms.

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

[0111] The present compound reacts with light even when used alone in a photosensitive composition. When a photoacid generator is added, the photosensitivity of the present compound is increased because the compound acts synergistically with the present compound in the photosensitive composition. Therefore, if the photosensitivity of a photosensitive composition composed only of the present compound is insufficient for the required specifications, it is preferable to add a photoacid generator. When the present photosensitive composition contains a photoacid generator, the content of the photoacid generator in the present photosensitive composition (the total amount when multiple photoacid generators are used in combination) is preferably 0.1 to 30 mass %, more preferably 0.5 to 20 mass %, and even more preferably 1 to 15 mass %, based on the total of the components of the photosensitive composition other than the solvent. When the content of the photoacid generator in the photosensitive composition is equal to or greater than the above-mentioned lower limit, the effect of enhancing photosensitivity can be obtained, whereas when the content is equal to or less than the above-mentioned upper limit, the composition is less susceptible to the poor film-forming properties of the photoacid generator, and therefore, good film-forming properties based on the photosensitive compound of the present invention can be obtained, which is preferable.

[0112] [solvent] The photosensitive composition generally 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 in the specification 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 used in combination, 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 appropriately 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] [Surfactants] The photosensitive composition preferably further contains a surfactant, preferably a fluorine-based and / or silicone-based surfactant. Examples of surfactants that fall into this category 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. Furthermore, surfactants other than fluorine-based and / or silicone-based surfactants can also be used, more specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, etc.

[0118] Other known surfactants may also be used as appropriate, such as those described in U.S. Patent Application Publication No. 2008 / 0248425A1, paragraphs

[0273] and thereafter.

[0119] The surfactants 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 of all 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 having 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. In particular, carboxylic acids are preferably used to improve performance, and aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred. The content of the carboxylic acid is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, and even more preferably from 0.01 to 3% by mass, based on the total amount of components other than the solvent in the photosensitive composition.

[0122] [Method for producing the present photosensitive composition] The photosensitive composition can be prepared by dissolving the compound, a photoacid generator, 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 the composition to actinic radiation, and developing the composition. More specifically, the method includes a step of applying the present photosensitive composition onto a substrate to form a photosensitive layer, a step of irradiating predetermined regions of the photosensitive layer with actinic radiation to perform pattern exposure, and a step of developing the exposed photosensitive layer to selectively remove exposed or unexposed areas of the photosensitive layer. The step of forming the photosensitive layer provides a substrate having a photosensitive layer, the step of pattern exposure provides a substrate having a latent image, and the step of development provides a substrate having a pattern layer.

[0124] [Photosensitive layer formation process] The photosensitive layer can be formed by applying the photosensitive composition to a substrate (e.g., silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit devices using a suitable coating method such as a spinner, and then drying at 50 to 150°C. In this case, if necessary, a commercially available inorganic or organic anti-reflective coating can be used, and further, an anti-reflective coating can be applied to the lower layer of the resist.

[0125] [Exposure process] In the present invention, unless otherwise specified, "exposure to actinic radiation" includes not only exposure to far ultraviolet light represented by a mercury lamp or an excimer laser, X-rays, extreme ultraviolet light (EUV light), and the like, but also exposure to writing using particle beams such as electron beams and ion beams. The exposure can be carried out by irradiating the formed photosensitive layer with actinic radiation in predetermined areas through a predetermined mask to perform pattern exposure, or by irradiating the layer with an electron beam to perform pattern exposure by drawing (direct drawing) without using a mask. The actinic radiation is not particularly limited, but examples thereof include KrF excimer laser, ArF excimer laser, extreme ultraviolet light (EUV light), and electron beams. Of these, extreme ultraviolet light (EUV light) and electron beams are preferred, and as described above, extreme ultraviolet light (EUV light) that emits 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 carried out by means of a conventional exposure / development machine, and may also be carried out using a hot plate or the like.

[0127] [Development process] After the 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> As the developer, an organic solvent is preferably used, preferably an organic solvent having a vapor pressure of 5 kPa or less at 20° C., 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; and 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. Of these, 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 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 amide solvents that can be used include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. As the sulfoxide solvent, for example, dimethyl sulfoxide can be used.

[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] The developer preferably contains at least one organic solvent selected from the group consisting of ester solvents having no hydroxyl groups in the molecule, ketone solvents having no hydroxyl groups in the molecule, and ether solvents, amide solvents, and sulfoxide solvents having no hydroxyl groups in the molecule.

[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 area, while an organic solvent with a solubility parameter of 11 or less can suppress the development rate of the pattern formation area, which is preferable. 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 for 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), di ... Ethylene 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 ) are used. 3 )1 / 2 or less, each independently containing at least 55% by volume of one or more solvents having a total Hansen solubility parameter δH+δP of at least about 16 (J / cm 3 ) 1 / 2, it is also possible to use developer compositions that contain from about 0.25% to about 45% by volume of one or more solvents.

[0142] The concentration of the organic solvent (total when multiple 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 preferable for the developer to consist essentially of an organic solvent. The term "consisting essentially of an organic solvent" includes the case where the developer contains trace amounts of a surfactant, antioxidant, stabilizer, 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, a suitable amount of a surfactant may be added to the developer used in the present invention. As the surfactant, the same surfactants as those used in the photosensitive composition of the present invention can be used. The amount of the surfactant used is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, and more preferably from 0.01 to 0.5% by mass, based on the total amount of the developer.

[0145] <Developing method> Examples of development methods that can be applied include a method in which the substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time (puddle method), a method in which developer is sprayed onto the surface of the substrate (spray method), and a method in which developer is continuously dispensed by scanning a developer dispensing nozzle at a constant speed over a substrate that is rotating at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while 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 unexposed or exposed areas of the photosensitive layer 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 from 0 to 50°C, more preferably from 15 to 35°C. The amount of developer can be adjusted appropriately depending on the development method.

[0146] [Rinse process] The present pattern formation method may include a step of washing with a rinse liquid containing an organic solvent after the development step.

[0147] <Rinse liquid> The organic solvent used in the rinse liquid preferably has a vapor pressure of 0.05 kPa to 5 kPa, more preferably 0.1 kPa to 5 kPa, and most preferably 0.12 kPa to 3 kPa at 20° C. By adjusting the vapor pressure of the organic solvent used in the rinse liquid to 0.05 kPa to 5 kPa, 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] As the rinse solution, various organic solvents can be used, but for the present compound, it is preferable to use a rinse solution containing water or at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, after development, a step of cleaning 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 step of cleaning 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 International Publication No. 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 solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents and hydrocarbon-based solvents used as the rinse liquid are the same as those explained above for the developer. It is particularly preferable to use a rinse solution containing at least one organic solvent selected from the group consisting of monohydric alcohol solvents, hydrocarbon solvents, and amide solvents.

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

[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 characteristics can be obtained.

[0152] The rinse solution may contain an appropriate amount of a surfactant. The surfactant may be the same as those used in the photosensitive composition described above, and the amount 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] <Rinse method> In the rinsing step, the developed pattern-formed substrate is washed with a rinsing liquid containing the organic solvent. The cleaning method is not particularly limited, but may be, for example, a method in which a rinse solution is continuously applied to a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with rinse solution for a certain period of time (dip method), or a method in which a rinse solution is sprayed onto the substrate surface (spray method). Of these, it is preferable to perform the cleaning process using the spin coating method, and then rotate the substrate at a rotation speed of 2000 to 4000 rpm after cleaning to remove the rinse solution from the substrate. The rotation time of the substrate can be set depending on the rotation speed within a range that achieves removal of the rinse solution from the substrate, but is usually 10 seconds to 3 minutes. Rinsing is preferably performed at room temperature. The rinsing time is preferably set so that the developing solvent does not remain on the substrate, and is usually preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C. The amount of the rinse solution can be adjusted appropriately depending on the rinse method.

[0154] [Post-processing process] After the development treatment or the rinsing treatment, a treatment can be carried out in which the developer or the rinsing liquid adhering to the pattern is removed using a supercritical fluid. Furthermore, after the development treatment, rinsing treatment, or treatment with a supercritical fluid, a heat treatment can be carried out 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, but are usually 40 to 160°C and 10 seconds to 3 minutes. The heat treatment may be carried out multiple times.

[0155] [Application] The photosensitive composition and the pattern forming method are suitable for use in producing semiconductor microcircuits, such as in the production of ultra-large-scale integrated circuits (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. [Example]

[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 1H-NMR was used to measure the

[0158] <Synthesis Example 1> Synthesis of triparatoluylbismuth (hereinafter sometimes referred to as Bi(p-Tol)3) Under a nitrogen atmosphere, para-toluyl bromide (43.40 g) in THF (100 mL) was added dropwise to magnesium flakes (6.66 g) to obtain a Grignard solution. A THF solution (150 mL) of BiCl3 (20.00 g) was prepared in an ice bath in a container, and the Grignard solution was added dropwise to the flask. The mixture was then stirred at room temperature for 90 minutes and then at 65°C for 20 minutes. To the reaction mixture, 3 mL of aqueous ammonium carbonate was added in an ice-water bath to quench the reaction. Further aqueous ammonium carbonate and ethyl acetate were added to extract the organic layer. The organic layer was dried over anhydrous MgSO4, and the solvent was removed under reduced pressure to obtain a residue. The resulting residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane (3:17) to obtain tripartite bismuth (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 mixture 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), tri-para-toluylbismuth (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] TIFF2026009009000017.tif41170

[0162] <Synthesis Example 4> Synthesis of Compound 2 A 100 mL recovery flask was charged with 1.30 g of 3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (Leap Chem), 1.50 g of Bi(p-Tol), and 18.5 mL of toluene, and the mixture was stirred at a bath temperature of 140°C for 4 hours and then at 150°C for 2 hours and 30 minutes. 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] TIFF2026009009000018.tif46170

[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 (Tokyo Chemical Industry Co., Ltd.), 6 mL of mesitylene (Tokyo Chemical Industry Co., Ltd.), and 6.00 g of 2,3-dimethylmaleic anhydride (Tokyo Chemical Industry Co., Ltd.) were placed in a 100 mL recovery flask equipped with a reflux condenser and stirred for a total of 73.5 hours at 165°C to 175°C. Because 2,3-dimethyl-1,3-butadiene was vaporized 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, and the mixture was left overnight. The precipitated solid was collected by filtration, washed with 5 mL of hexane, and dried to obtain 7.0 g of a brown solid. GC-MS analysis of this solid confirmed that it was the desired 3a,5,6,7a-tetramethyl-4,7-dihydroisobenzofuran-1,3-dione. 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 (Fujifilm Wako Pure Chemical Industries, Ltd.), stirred at room temperature to dissolve, and then stirred at 120 °C for 40 minutes. After cooling to room temperature, 100 mL of 1N hydrochloric acid (Kishida Chemical Co., Ltd.) and 50 mL of dichloromethane were added for separation and washing. The oil phase was dried over magnesium sulfate and filtered through a short column packed with silica gel. The dichloromethane was removed under reduced pressure, yielding 6.4 g of the desired 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),2.0~1.9(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 were placed 1.05 g of 6-methoxycarbonyl-1,3,4,6-tetramethyl-cyclohex-3-ene-1-carboxylic acid, 0.66 g of Bi(p-Tol), and 5 mL of tetrahydrofuran, and 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),1.95~1.85(m,2H),1.6~1.4(br.m,6H),1.3~1.1(m,6H).

[0167] TIFF2026009009000019.tif47170

[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. The mixture was then 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 resulting solid identified it as 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] TIFF2026009009000020.tif56161

[0170] <Synthesis Example 9> Synthesis of Compound 5 Under a nitrogen atmosphere, 1.5 g (3.11 mmol) of tris-para-toluylbismuth, 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. The mixture was then cooled to room temperature, and the solvent was concentrated under reduced pressure to obtain a white powder (2.08 g) as the residue. NMR analysis of the resulting solid identified it as 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] TIFF2026009009000021.tif58161

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

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

[0174] <Developing> 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 Examples 1 to 5, respectively.

[0175] <Resolution evaluation> Resolution was evaluated using an electron beam lithography system. 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 was given for cases where the line and space pattern was visible, a rating of "B" for cases where the pattern was visible but partially crosslinked, and a rating of "C" for cases where the pattern was not visible. 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] [Table 1]

[0178] <Sensitivity measurement> 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 ) is higher, and higher exposure is lower. The results are shown in Table 2.

[0179] [Table 2]

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

[0181] [result] From the results of electron beam (EB) writing tests, 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 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 to stand at room temperature to carry out a stability test of the resist solutions. The results are shown in Table 3. The resist solutions of Compounds 1 to 5 did not produce any 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 stability in resist solutions.

[0183] [Table 3]

[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 is suitable, wherein the carboxylate ligand A has a cyclic structure that is bonded to a carboxylate group, the carbon C1 in the cyclic structure that is bonded to the carboxylate group is a tertiary or quaternary carbon, and the carbon C2 adjacent to the carbon C1 in the cyclic structure is a substituent R 1 and the substituent R 1 Compounds in which is an organic group or a halogen atom are highly sensitive to EUV, have high resolution, and the resist solution is stable and can be stored for a long period of time, making them 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, The carboxylate ligand A has a cyclic structure that bonds to the carboxylate group, and the carbon C in the cyclic structure that bonds to the carboxylate group １ is a tertiary or quaternary carbon, Carbon C in the ring structure 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; compound.

2. The compound of claim 1 , wherein the cyclic structure has 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. n is an integer from 2 to 8, and a plurality of A 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. n is an integer from 2 to 7, and a plurality of A 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 non-metallic 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 any one of a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, and 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 with halogen, 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 may contain unsaturated hydrocarbons or halogen atoms. x is an integer of 1 to 3.

14. The substituent R in the general formula (3) ３ is a methyl group, and 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 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. n is an integer from 2 to 7, and a plurality of A 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 a substituent R １ｂ may be the same as or different from. n is an integer from 2 to 7, and a plurality of A 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. 2. A cluster compound according to claim 1, which has a plurality of the metal atoms, wherein the plurality of metal atoms have a metal-metal bond or are bonded to each other via 1 to 3 atoms.

20. 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. n is an integer from 2 to 7, and a plurality of A 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. 21. The cluster compound of claim 20, wherein the metal atom is a non-metallic atom.

22. 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 structure of a carboxylate ligand A in a solution.

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

25. 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 according to any one of claims 1 to 18 and the cluster compound according to any one of claims 19 to 22, in a concentration of 50 to 100 mass percent of the total solids.

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

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

29. 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, comprising forming a pattern layer by the pattern formation method according to claim 28.

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