Transition metal cluster compound, method for producing said compound, photosensitive composition containing said compound, pattern forming method using said composition, substrate, and method for producing substrate

Abstract

Provided are a transition metal cluster compound capable of achieving miniaturization of a circuit pattern, a photosensitive composition containing the same, and so forth.　A transition metal cluster compound according to the present invention is characterized by containing transition metal atoms and carboxylate ligands A each having an alicyclic structure of saturated hydrocarbons. Preferably, the carboxylate ligand A contains an alicyclic structure of saturated hydrocarbons, which has at least one substituent R, the substituent R is an organic group or a halogen atom, and the alicyclic structure has 3-10 carbon atoms.

Description

Transition metal cluster compound, method for producing the compound, photosensitive composition containing the compound, pattern forming method using the composition, substrate, and method for producing the substrate

[0001] The present invention relates to a transition metal cluster compound suitable for use in ultra-microlithography processes such as 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.

[0002] In the manufacturing process of semiconductor devices, microfabrication is carried out by lithography using a photoresist composition. In semiconductor photolithography, in accordance with Moore's Law, circuit patterns become smaller as semiconductor devices become smaller, and further miniaturization is desired.

[0003] 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.

[0004] Therefore, non-chemically amplified photoresists (hereinafter referred to as metal-containing resists) primarily composed of compounds containing metal elements such as Zn and Sn have been proposed in recent years. In metal-containing resists, the metal component itself is a photosensitive substance and functions as a base material. Because they do not involve acid diffusion, they can improve line edge roughness, making them promising next-generation resist materials for forming finer pattern structures. It has been reported that fine patterns can actually be formed using next-generation exposure equipment using extreme ultraviolet (EUV) light. 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 (EUV) light, electron beams, or the like. Patent Document 6 describes a transition metal cluster compound composed of a transition metal element and a carboxy ligand containing an alicyclic structure with a double bond, but does not disclose that when the alicyclic structure is composed of multiple rings, all of the chemical structures of the multiple rings are composed of saturated hydrocarbons.

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

[0006] Minoru Toriumi etc.,Proc.SPIE,9779(2016)97790GLianjia Wu etc.,Proc.SPIE,10957(2019)109570BNeha Thakur etc.,Proc.SPIE,10957(2019)10957D

[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 for a photoresist that is compatible with ultrafine patterns.

[0009] Therefore, an object of the present invention is to provide a transition metal cluster compound that can realize finer circuit patterns, a photosensitive composition containing the same, 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.

[0010] The present invention has the following aspects [1] to

[19] .

[0011] [1] A transition metal cluster compound comprising a transition metal atom and a carboxylate ligand A having an alicyclic structure of a saturated hydrocarbon.

[0012] [2] The transition metal cluster compound according to [1], wherein the carboxylate ligand A comprises an alicyclic structure of a saturated hydrocarbon having at least one substituent R, and the substituent R is an organic group or a halogen atom.

[0013] [3] The transition metal cluster compound according to [1] or [2], wherein the alicyclic structure of the carboxylate ligand A has 3 to 10 carbon atoms.

[0014] [4] The transition metal cluster compound according to any one of [1] to [3], wherein the transition metal atoms are comprised of 2 to 20 atoms.

[0015] [5] The transition metal cluster compound according to any one of [1] to [4], wherein the transition metal atom is any one of titanium, hafnium, and zirconium.

[0016] [6] The transition metal cluster compound according to any one of [1] to [5], wherein the alicyclic structure of the carboxylate ligand A is a cyclopropane ring, a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, or a norbornane ring.

[0017] [7]. The carbon C in the alicyclic structure to which the carboxylate group of the carboxylate ligand A is bonded １ is a tertiary or quaternary carbon atom and is one of the carbon atoms constituting the cyclic structure of the alicyclic structure.

[0018] [8] The transition metal cluster compound according to any one of claims [2] to [7], wherein the substituent R is an organic group having 1 to 10 carbon atoms.

[0019] [9] The transition metal cluster compound according to any one of [2] to [8], wherein the organic group is any one of a hydrocarbon group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group.

[0020]

[10] The transition metal cluster compound according to any one of [2] to [9], wherein the structure of the substituent R does not contain an unsaturated hydrocarbon or aromatic group.

[0021]

[11] A method for producing a transition metal cluster compound according to any one of [1] to

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

[0022]

[12] A photosensitive composition comprising the transition metal cluster compound according to any one of [1] to

[10] .

[0023]

[13] The photosensitive composition according to

[12] , further comprising a solvent.

[0024]

[14] The photosensitive composition according to

[12] or

[13] , characterized in that it contains the transition metal cluster compound according to any one of [1] to

[10] in a concentration of 50 to 100 mass % of the total solids.

[0025]

[15] The photosensitive composition according to any one of

[12] to

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

[0026]

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

[12] to

[15] to a substrate, exposing the applied photosensitive composition to actinic radiation, and developing the exposed photosensitive composition.

[0027]

[17] The pattern formation method according to

[16] , 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.

[0028]

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

[16] or

[17] .

[0029]

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

[16] or

[17] .

[0030] The transition metal cluster compound of the present invention contains a transition metal atom and a carboxylate ligand A having an alicyclic structure of a saturated hydrocarbon, and is therefore considered to be an excellent semiconductor photoresist material that can be produced relatively easily by organic synthesis and exhibits high sensitivity when exposed to actinic radiation. Detailed Description of the Invention

[0031] The present invention will be described below based on one embodiment. However, the present invention is not limited to this embodiment. Note that, although the present specification uses "to" to express a numerical range from a lower limit value to an upper limit value, 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 and the upper limit value.

[0032] [Transition Metal Cluster Compound] A transition metal cluster compound according to one embodiment of the present invention (hereinafter also referred to as the present cluster compound) is a compound forming a cluster centered around a transition metal atom, and is a compound containing a transition metal atom and a carboxylate ligand A having an alicyclic structure of a saturated hydrocarbon. The carboxylate ligand A has a carboxylate group bonded to the alicyclic structure. When the alicyclic structure of the saturated hydrocarbon contained in the carboxylate ligand A is composed of multiple six-membered rings, it is preferable that all of the chemical structures of the multiple rings are composed of saturated hydrocarbons. When the alicyclic structure is not a six-membered ring, it is not necessary that all of the chemical structures of the multiple rings are composed of saturated hydrocarbons.

[0033] In the present invention, a cluster compound refers to a metal complex molecule having a metal atom and a ligand, in which multiple metal atoms are bonded to each other directly or through a bridging ligand. This includes compounds having multiple metal atoms, in which the metal atoms are bonded to each other via metal-metal bonds or via one to three atoms. The cluster compound may contain oxygen and / or hydroxyl groups within the cluster compound structure, preferably a μ-oxo ligand (—O—) in which an oxygen atom is coordinated between metal atoms and / or a hydroxyl group (—OH) in which a hydroxyl group is coordinated to a metal. A carboxylate ligand is a ligand having at least one carboxylate group, and a carboxylate group is a functional group having the chemical structure —C(═O)O—. To more effectively achieve the effects of the present invention, a ligand having only one carboxylate group is preferred.

[0034] The transition metal atoms in the present cluster compound are preferably composed of 20 or less atoms, in order to provide high solubility in a developer before exposure to actinic radiation, and are preferably composed of 2 or more atoms, and more preferably composed of 4 to 12 atoms, in order to provide high insolubility in a developer after exposure to actinic radiation.

[0035] Examples of the transition metal atoms include elements from Period 4 or higher and Groups 3 to 12 of the Periodic Table. Among these, titanium, hafnium, and zirconium are preferred in terms of ease of production by organic synthesis. Two or more types of the transition metal atoms may be used in combination.

[0036] The present cluster compound contains a carboxylate ligand A, and this carboxylate ligand A has an alicyclic structure of a saturated hydrocarbon. From the viewpoint of ease of production by organic synthesis, the alicyclic structure of the saturated hydrocarbon is preferably composed of 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and particularly preferably 3 to 5 carbon atoms. Examples of the alicyclic structure of the saturated hydrocarbon include a cycloalkyl ring. From the viewpoint of ease of production by organic synthesis, the cycloalkyl ring is preferably a cycloalkyl ring having 3 to 10 carbon atoms, more preferably a cycloalkyl ring having 3 to 8 carbon atoms, even more preferably a cycloalkyl ring having 3 to 6 carbon atoms, and particularly preferably a cycloalkyl ring having 3 to 5 carbon atoms. Specifically, any of a cyclopropane ring, a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, and a norbornane ring is preferred. From the viewpoint of ease of removal upon exposure and stability when not exposed, the carboxylate ligand A has an alicyclic structure bonded to a carboxylate group, and of the alicyclic structure, the carbon C in the alicyclic structure bonded to the carboxylate group is preferably a cycloalkyl ring having 3 to 10 carbon atoms, even more preferably a cycloalkyl ring having 3 to 8 carbon atoms, even more preferably a cycloalkyl ring having 3 to 6 carbon atoms, and particularly preferably a cycloalkyl ring having 3 to 5 carbon atoms. １ is preferably a tertiary or quaternary carbon, and most preferably a tertiary carbon. １ is preferably one of the carbon atoms constituting the cyclic structure of the alicyclic structure.

[0037] Furthermore, the carboxylate ligand A may have one or more substituents R in the alicyclic structure of the saturated hydrocarbon. The substituent R is an organic group or a halogen atom, and the organic group may contain a halogen atom or a heteroatom. Examples of the organic group include hydrocarbon groups such as alkyl groups and cycloalkyl groups, aromatic groups, ester groups, sulfonyl groups, alkoxy groups, amide groups, amino groups, and carbonyl oxygen groups. The substituent R preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and particularly preferably 1 to 3. Specific examples of the substituent R include hydrocarbon groups such as linear alkyl groups such as methyl groups and ethyl groups, branched alkyl groups such as isopropyl groups and butyl groups, halogenated alkyl groups such as halogenated methyl groups, halogenated ethyl groups, and halogenated propyl groups, and cycloalkyl groups such as cyclopropyl groups and cyclobutyl groups. Examples of aromatic groups include aryl groups such as phenyl groups and naphthyl groups, arylalkyl groups, and alkylaryl groups. When the organic group contains a heteroatom, examples of the organic group include ester groups, sulfonyl groups, alkoxy groups, amide groups, amino groups, and carbonyl oxygen groups. Examples of heteroatoms include oxygen, nitrogen, phosphorus, sulfur, and silicon. Examples of ester groups include alkyl ester groups such as acetyl, ethyl ester, and n-propyl ester, and aromatic ester groups such as phenyl ester. Examples of sulfonyl groups include alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, and n-propylsulfonyl. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, and phenoxy. Examples of amino groups include amino alkyl groups such as amino (-NH), aminomethyl (NH-CH-), aminoethyl (NH-C-H-), and aminopropyl (NH-C-H-), and dialkylamino groups such as dimethylamino ((CH)N-) and diethylamino ((C-H)N-). Examples of the amide group include alkylamide groups such as methylamide ((CH)N(C=O)-) and ethylamide ((CH)N(C=O)-), as well as carbonyl oxygen groups (C=O).The substituent R may contain an unsaturated hydrocarbon in its structure. Examples of the halogen atom include fluorine, chlorine, and bromine.

[0038] In terms of film formability, exposure sensitivity, and solvent solubility, the substituent R is preferably a saturated hydrocarbon group, and particularly preferably an alkyl group. Furthermore, it is preferable that the structure of the substituent R does not contain an unsaturated hydrocarbon or aromatic group. This is because, 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 A in the present cluster 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. Furthermore, when the carboxylate ligand A in the present cluster compound is replaced with a carboxylate ligand having an alicyclic structure of an unsaturated hydrocarbon, the unsaturated hydrocarbon tends to undergo unintended chain reactions due to radicals generated after exposure, resulting in roughness. Furthermore, it is most preferable that the carboxylate ligand A does not have a substituent R.

[0039] The structure of the carboxylate ligand A can be analyzed by known techniques, for example, by NMR.

[0040] The molecular weight of the present cluster compound is preferably 1000 to 8000, more preferably 1000 to 6000, and particularly preferably 1500 to 5000. If the molecular weight of the present cluster compound is below the upper limit, the volume is small, and therefore roughness and resolution are expected to be improved. On the other hand, if the molecular weight is above the lower limit, coating properties and etching resistance tend to be improved. Note that this molecular weight is a guideline and does not determine lithography properties by itself, so it is not limited to this. The molecular weight of the present cluster compound can be analyzed by known techniques, for example, by NMR.

[0041] [Production Method] The present cluster compound can be produced, for example, by reacting a compound containing a transition metal atom with a carboxylic acid having a structure of carboxylate ligand A in a solution. As an example, the present cluster compound can be produced by reacting a solution containing a compound containing a transition metal atom with a carboxylic acid having a structure of carboxylate ligand A.

[0042] Examples of compounds containing transition metal atoms include organic compounds containing transition metal atoms, such as metal alkoxides, and specific examples include zirconium normal propoxide, zirconium tertiary butoxide, hafnium normal propoxide, and hafnium tertiary butoxide.

[0043] Examples of carboxylic acids having the structure of carboxylate ligand A include carboxylic acids in which a carboxy group is bonded to an alicyclic structure made of saturated hydrocarbon. The carboxylic acid exemplified by the following general formula (1) has an alicyclic structure made of saturated hydrocarbon consisting of six carbon atoms, with a carboxy group bonded to one carbon atom and a substituent bonded to another carbon atom.

[0044]

[0045] 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), and more specific examples include cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 2-methyl-1-cyclohexanecarboxylic acid, 3-methyl-1-cyclohexanecarboxylic acid, and 3-oxocyclobutane-1-carboxylic acid.

[0046] To explain the production method in more detail, the method can be carried out by placing a solution containing a compound containing a transition metal atom and a carboxylic acid having a structure of carboxylate ligand A in a reaction vessel and stirring them. A solvent may be added to dissolve the raw materials.

[0047] 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 1 to 24 hours. In the present invention, room temperature is approximately 1 to 30°C.

[0048] If the product precipitates or crystallizes after the reaction, it can be filtered to obtain the cluster compound. 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.

[0049] The reaction vessel is preferably a sealed vessel, and for small amounts, a Schlenk tube or the like can be used, and 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 under a nitrogen or argon atmosphere.

[0050] The solution containing the compound containing a transition metal atom and the carboxylic acid having the structure of carboxylate ligand A are preferably mixed in a ratio of 1:2 to 1:4, more preferably 1:4, in terms of the amount of substances.

[0051] [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 cluster compound. The photosensitive composition may contain only one type of the present cluster compound, or two or more types. The content of the present cluster compound in the present photosensitive composition is 50 to 100% by mass, preferably 60 to 100% by mass, and particularly preferably 70 to 90% by mass, of the total solids of the photosensitive composition. The total solids refer to the solid obtained by evaporating the photosensitive composition to dryness, for example. The concentration of the present cluster compound in the present photosensitive composition is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and particularly preferably 1 to 40% by mass. When the content of the present cluster compound in the present photosensitive composition is equal to or greater than the above-mentioned lower limit, good exposure sensitivity can be obtained.

[0052] [Photoacid Generator] The photosensitive composition can also function by containing, together with the cluster compound, a photoacid generator that generates an acid when exposed to 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, however, 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.

[0053] The photoacid generator that generates an acid when exposed to actinic radiation is not particularly limited as long as it is a known compound, but is preferably a compound that generates an organic acid, such as at least one of sulfonic acid, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide, when exposed to actinic radiation.

[0054] 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.

[0055] Examples of the embodiment (1) include a combined use of a sulfonic acid generator having fluorine and a tris(fluoroalkylsulfonyl)methide acid generator, a combined use of a sulfonic acid generator having fluorine and a sulfonic acid generator not having fluorine, and a combined use of an alkylsulfonic acid generator and an arylsulfonic acid generator.

[0056] An example of the embodiment (2) is the combined use of two acid generators whose generated acid anions differ in the number of carbon atoms by 4 or more.

[0057] The photosensitive composition is preferably a photosensitive composition for use 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 a certain period of development. Examples of actinic radiation include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0058] As for actinic radiation, a shorter wavelength is preferred because higher resolution can be obtained, and actinic radiation with a wavelength of 6 nm or more and 15 nm or less is preferred, and more preferably 6.5 nm or less and 13.5 nm or less is preferred. In other words, extreme ultraviolet (EUV light) is preferred. In other words, the present photosensitive composition is preferably a photosensitive composition that reacts when exposed to actinic radiation with a wavelength of 6 nm or more and 15 nm or less. "Reaction" means that the photosensitive composition absorbs the irradiated actinic radiation and is modified by the generated active species such as radicals and ions.

[0059] The present cluster compound reacts with light even when used alone in a photosensitive composition. When a photoacid generator is added, it acts synergistically with the present cluster compound in the photosensitive composition to enhance the photosensitivity of the present cluster compound. Therefore, if the photosensitivity of a photosensitive composition composed only of the present cluster compound is insufficient for the required specifications, it is preferable to add a photoacid generator.

[0060] When the present photosensitive composition contains a photoacid generator, the content of the photoacid generator in the present photosensitive composition (the total amount when a plurality of 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 amount of the components other than the solvent in the photosensitive composition.

[0061] 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.

[0062] [Solvent] The present photosensitive composition usually contains a solvent for preparing the composition. The solvent for preparing the photosensitive composition is not particularly limited as long as it dissolves each component, and examples thereof include toluene, alkylene glycol monoalkyl ether carboxylates (such as propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxypropane)), alkylene glycol monoalkyl ethers (such as propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)), alkyl lactate esters (such as ethyl lactate and methyl lactate), cyclic lactones (such as γ-butyrolactone, preferably having 4 to 10 carbon atoms), linear or cyclic ketones (such as 2-heptanone and cyclohexanone, preferably having 4 to 10 carbon atoms), alkylene carbonates (such as ethylene carbonate and propylene carbonate), alkyl carboxylates (preferably alkyl acetates such as butyl acetate), alkyl alkoxyacetates (ethyl ethoxypropionate), alkylamides (N,N-dimethylformamide), and alkyl sulfoxides (dimethyl sulfoxide). Other usable solvents include, for example, the solvents described in paragraphs

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

[0063] 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. These solvents may be used alone or in combination of two or more. When two or more solvents are mixed, it is preferred to mix a solvent having a hydroxyl group with a solvent not having a hydroxyl group.

[0064] 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.

[0065] The solvent for the present photosensitive composition preferably has a solubility parameter (SP value) of 7.5 to 11, and more preferably 8 to 11. The solubility parameter (SP value) will be described later. The content of the solvent in the total amount of the present 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 %.

[0066] [Surfactant] The photosensitive composition preferably further contains a surfactant. The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of such surfactants include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, Inc., PF656 and PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., Fluorad FC430 manufactured by Sumitomo 3M Limited, and Polysiloxane Polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0067] Surfactants other than fluorine-based and / or silicone-based surfactants can also be used. More specifically, examples include polyoxyethylene alkyl ethers and polyoxyethylene alkylaryl ethers. Other known surfactants can also be used as appropriate. Usable surfactants include, for example, those described in paragraphs

[0273] and following in U.S. Patent Application Publication No. 2008 / 0248425 A1. The surfactants may be used alone or in combination of two or more. 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 amount of components of the photosensitive composition other than the solvent.

[0068] [Resin] The photosensitive composition can be used alone to form a pattern, but it may also contain a resin material in addition to the cluster compound. The resin material is not particularly limited as long as it dissolves in a solvent, and examples include novolac resin, styrene resin, and acrylic resin. These resins may contain one or more copolymers.

[0069] These resins may be used alone or in combination of two or more, and may contain, in their molecular structure, dissolution-inhibiting groups that decompose when exposed to chemically active species such as acids or radicals, or crosslinking groups that crosslink. Examples of dissolution-inhibiting groups that decompose when exposed to chemically active species such as acids or radicals include alkoxycarbonyl groups and acetal groups. Examples of crosslinking groups that crosslink when exposed to 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.

[0070] [Other Additives] In addition to the components described above, the photosensitive composition may contain, as appropriate, carboxylic acids, carboxylic acid onium salts, dissolution-inhibiting compounds with a molecular weight of 3,000 or less as described in, for example, Proceedings of SPIE, 2724, 355 (1996), dyes, plasticizers, photosensitizers, light absorbers, crosslinking agents, antioxidants, and the like. Carboxylic acids are particularly preferred for improving performance. Preferred carboxylic acids include aromatic carboxylic acids such as benzoic acid and naphthoic acid. The carboxylic acid content is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, based on the total weight of the components of the photosensitive composition other than the solvent.

[0071] [Method for Producing the Photosensitive Composition] The photosensitive composition can be produced by dissolving the cluster compound, a photoacid generator (if used) and other components in a solvent for preparation, and filtering the solution through a filter, if necessary. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon, with 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.

[0072] [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 applied photosensitive composition to actinic radiation, and developing the exposed photosensitive composition. More specifically, the steps comprise the steps of applying the present photosensitive composition to a substrate to form a photosensitive layer, irradiating predetermined regions of the photosensitive layer with actinic radiation to perform pattern exposure, and developing the exposed photosensitive layer to selectively remove exposed or unexposed regions of the photosensitive layer. The photosensitive layer forming step provides a substrate having a photosensitive layer. The pattern exposure step provides a substrate having a photosensitive layer with a latent image. The development step provides a substrate having a patterned layer.

[0073] [Photosensitive Layer Formation Step] The photosensitive layer can be formed by applying the photosensitive composition to a substrate (e.g., silicon or silicon dioxide coated) such as those used in the manufacture of integrated circuit devices using a suitable coating method such as a spinner, followed by drying at 50 to 150°C. In this case, a commercially available inorganic or organic antireflective film can be used, if necessary. Furthermore, an antireflective film can be applied as an underlayer of the resist.

[0074] [Exposure Step] In the present invention, unless otherwise specified, "exposure to actinic radiation" includes not only exposure with far ultraviolet light typified by mercury lamps and excimer lasers, X-rays, extreme ultraviolet light (EUV light), and the like, but also exposure with particle beams such as electron beams and ion beams. Exposure can be performed by irradiating predetermined regions of the formed photosensitive layer with actinic radiation through a predetermined mask to perform pattern exposure, or by irradiating with an electron beam to perform pattern exposure without using a mask (direct writing). The actinic radiation is not particularly limited, but examples include KrF excimer lasers, ArF excimer lasers, extreme ultraviolet light (EUV light), and electron beams. Extreme ultraviolet light (EUV light) and electron beams are preferred, and as described above, extreme ultraviolet light (EUV light) emitting actinic radiation with a wavelength of 6 nm to 15 nm is preferred.

[0075] After the exposure, baking (heating) may or may not be performed before development. When baking (heating) is performed, the heating temperature is preferably 50 to 200°C, more preferably 60 to 180°C, and even more preferably 80 to 150°C. When baking (heating) is performed, the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.

[0076] [Development Step] After exposure, development is carried out to selectively remove the exposed or unexposed areas of the photosensitive layer. As a development method, a known method can be adopted, for example, a method using a gas or a method using a developer.

[0077] <Developer> It is preferable to use an organic solvent as the developer, and one having a vapor pressure of 5 kPa or less at 20° C. is preferred, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic solvent to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, improving the temperature uniformity within the surface of the pattern-formed substrate, and as a result, improving the dimensional uniformity within the surface of the pattern-formed substrate.

[0078] 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.

[0079] Examples of ester-based solvents include alkyl carboxylate solvents such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl-3-ethoxypropionate, propylene glycol diacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, and propyl lactate; alkylene glycol monoalkyl ether carboxylate solvents such as propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and propylene glycol monoethyl ether acetate; and butyl acetate, amyl acetate, ethyl lactate, and propylene glycol monomethyl ether acetate are more preferred.

[0080] 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.

[0081] Examples of alcohol-based solvents include 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 alcohol such as n-hexyl alcohol, heptyl alcohol such as n-heptyl alcohol, octyl alcohol 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. Examples of suitable solvents include alkylene glycol monoalkyl ether 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 solvents such as methoxymethylbutanol and propylene glycol dimethyl ether, and phenolic solvents such as phenol and cresol, with 1-hexanol, 2-hexanol, 1-octanol, 2-ethylhexanol, propylene glycol monomethyl ether, and cresol being more preferred. Examples of suitable amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone.

[0082] As the sulfoxide solvent, for example, dimethyl sulfoxide can be used.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] As the developer, it is preferable to use a developer containing at least one organic solvent selected from the group consisting of ester solvents having no hydroxyl groups in the molecule, ketone solvents having no hydroxyl groups in the molecule, and ether solvents having no hydroxyl groups in the molecule, amide solvents, and sulfoxide solvents.

[0087] The organic solvent used as the developer in the present invention is preferably an organic solvent having a solubility parameter (SP value) of 7.5 or more and 11 or less. An organic solvent with a solubility parameter of 7.5 or more increases the development rate of the dissolved portion, while an organic solvent with a solubility parameter of 11 or less can suppress the development rate of the pattern formation portion, and is therefore preferred. The solubility parameter of the organic solvent of the developer is more preferably 8 or more and 11 or less.

[0088] In the present invention, the solubility parameter (SP value) is calculated by the method proposed by Fedors et al. Specifically, the value is determined by referring to "POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (pp. 147-154)." The SP value is a physical property determined by the content of hydrophobic and hydrophilic groups in the molecule, and when a mixed solvent is used, the SP value refers to the value of the mixture.

[0089] Examples of organic solvents that satisfy the above SP values ​​include diethylene glycol monomethyl ether (SP value = 10.7), triethylene glycol monomethyl ether (SP value = 10.7), ethylene glycol monoisopropyl ether (SP value = 10.9), ethylene glycol monobutyl ether (SP value = 10.2), diethylene glycol monobutyl ether (SP value = 10.0), triethylene glycol monobutyl ether (SP value = 10.0), ethylene glycol monoisobutyl ether (SP value = 9.1), ethylene glycol monohexyl ether (SP value = 9.9), diethylene glycol monohexyl ether (SP value = 9.7), diethylene glycol mono-2-ethylhexyl ether (SP value = 9.3), ethylene glycol monoallyl ether (SP value = 10.8), ethylene glycol monophenyl ether (SP value = 10.8), ethylene glycol monobenzyl ether (SP value = 10.9), propylene glycol monomethyl ether (SP value = 10.0), dipropylene glycol Cholesterol 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 (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), dipropylene glycol monomethyl ether acetate (SP value = 9.2), etc. The above organic solvents may be used in combination, or may be used in combination with a solvent other than those listed above or with water.For example, as described in WO 2020 / 210660, at least two solvents each independently have a sum of Hansen solubility parameters δH + δP of about 16 (J / cm. ３ ) 1 / 2 or less, each independently having a sum of Hansen solubility parameters δH + δP of at least about 16 (J / cm ３ ) 1 / 2, it is also possible to use developer compositions that include from about 0.25% to about 45% by volume of one or more solvents.

[0090] The concentration of the organic solvent (total when a plurality of organic solvents are mixed) in the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. It is particularly preferred that the developer essentially consists of an organic solvent. The term "essentially consisting of an organic solvent" includes the case where the developer contains trace amounts of a surfactant, an antioxidant, a stabilizer, an antifoaming agent, etc.

[0091] 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.

[0092] If necessary, an appropriate amount of a surfactant can be added to the developer used in the present invention. The surfactant may be the same as those described above as surfactants used in the photosensitive composition of the present invention. The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

[0093] <Developing Method> Examples of the developing method that can be applied include a method of immersing a substrate in a tank filled with a developer for a certain period of time (dipping method), a method of piling up a developer on the surface of the substrate by surface tension and leaving it to stand for a certain period of time to perform development (puddling method), a method of spraying a developer onto the surface of the substrate (spraying method), and a method of continuously dispensing developer while scanning a developer dispensing nozzle at a constant speed onto a substrate that is rotating at a constant speed (dynamic dispensing method).

[0094] Furthermore, 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 cluster 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 0 to 50°C, more preferably 15 to 35°C. The amount of developer can be adjusted appropriately depending on the development method.

[0095] [Rinsing Step] The pattern forming method of the present invention may include, after the developing step, a step of washing with a rinse liquid containing an organic solvent.

[0096] <Rinse Liquid> The organic solvent used in the rinse liquid preferably has a vapor pressure of 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less at 20° C. By adjusting the vapor pressure of the organic solvent used in the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is improved, and further swelling due to penetration of the rinse liquid is suppressed, improving the dimensional uniformity within the wafer surface.

[0097] Various organic solvents can be used as the rinse solution. For the present cluster compound, it is preferable to use a rinse solution containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents, or water. More preferably, after development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. Even more preferably, after development, a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of alcohol solvents and hydrocarbon solvents. For example, as described in 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.

[0098] Specific examples of the ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, ether-based solvent, and hydrocarbon-based solvent used as the rinse solution are the same as those described above for the developer. Particularly preferably, a rinse solution containing at least one organic solvent selected from the group consisting of monohydric alcohol-based solvents, hydrocarbon-based solvents, and amide-based solvents is used.

[0099] 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.

[0100] Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as octane, decane, and dodecane. Examples of amide solvents that can be used include N,N-dimethylformamide. The above-mentioned components may be mixed in plural, or may be mixed with organic solvents other than those mentioned above.

[0101] The organic solvent may be mixed with water, but the water content in the rinse solution is usually 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Most preferably, the rinse solution does not contain water. By keeping the water content at 30% by mass or less, good development properties can be obtained.

[0102] The rinse solution may contain an appropriate amount of a surfactant, which may be the same as those used in the photosensitive composition described above, and the amount of surfactant used is usually 0.001 to 5 mass %, preferably 0.005 to 2 mass %, and more preferably 0.01 to 0.5 mass %, based on the total amount of the rinse solution.

[0103] <Rinsing Method> In the rinsing step, the developed pattern-formed substrate is washed with a rinse solution containing the organic solvent. The washing method is not particularly limited, but examples include a method in which the rinse solution is continuously applied to a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in a tank filled with the rinse solution for a certain period of time (dipping method), and a method in which the rinse solution is sprayed onto the substrate surface (spray method). Among these, it is preferable to perform the washing process using the spin coating method, and then rotate the substrate at a rotation speed of 2000 to 4000 rpm after washing to remove the rinse solution from the substrate. The substrate rotation time can be set depending on the rotation speed within a range that achieves removal of the rinse solution from the substrate, but is typically 10 seconds to 3 minutes. Rinsing is preferably performed at room temperature.

[0104] The rinsing time is preferably set so that no developing solvent remains on the substrate, and is usually preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the rinsing liquid is preferably 0 to 50°C, more preferably 15 to 35°C. The amount of rinsing liquid can be adjusted appropriately depending on the rinsing method.

[0105] [Post-treatment Step] After the development treatment or rinsing treatment, a treatment can be performed using a supercritical fluid to remove the developer or rinsing solution adhering to the pattern. Furthermore, after the development treatment, rinsing treatment, or treatment with a supercritical fluid, a heat treatment can be performed to remove the solvent remaining in the pattern. The heating temperature and time are not particularly limited as long as a good resist pattern can be obtained, and are usually 40 to 160°C and 10 seconds to 3 minutes. The heat treatment can be performed multiple times.

[0106] [Uses] The photosensitive composition and the patterning method are suitable for use in the production of semiconductor microcircuits, such as in the production of VLSIs and high-capacity microchips, and can produce substrates having patterned layers. During the production of semiconductor microcircuits, the resist film on which the pattern is formed is subjected to circuit formation and etching, and the remaining resist film portion is ultimately removed with a solvent or the like.

[0107] 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.

[0108] The following compounds 1 to 3 were prepared to obtain Examples 1 to 3. The composition and ligand structure of each compound are as follows: １ Measured by H-NMR.

[0109] <Compound 1> 10 g of zirconium (IV) tetrapropoxide (70% 1-propanol solution, manufactured by Tokyo Chemical Industry Co., Ltd.), 10.1 g of cyclohexanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 20 mL of hexane were placed in a 100 mL recovery flask and stirred at 90°C for 1 hour. After cooling to room temperature, 150 mL of methanol was added, and the mixture was concentrated under reduced pressure until approximately 90% of the solvent was removed, resulting in the precipitation of a solid. The supernatant was decanted, and the solid was washed twice with 100 mL of methanol and then dried, yielding 5.0 g of Compound 2 as a white solid. 1 H-NMR (CDCl3) δ2.5~1.0 (highly broadnend peak)

[0110]

[0111] <Compound 2> 50 g of zirconium (IV) tetrapropoxide (70% 1-propanol solution, manufactured by Tokyo Chemical Industry Co., Ltd.), 64.1 g of cyclobutanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 50 mL of toluene were placed in a 500 mL recovery flask and stirred for 4 hours at 100° C. Thereafter, the mixture was cooled to room temperature, concentrated under reduced pressure, and a small amount of acetonitrile was added, followed by cooling to below 0° C., thereby obtaining 18.6 g of precipitated Compound 2 as a white solid. 1 H-NMR (CDCl3) δ 3.19-2.88 (12H, m), 2.37-1.75 (72H, m) ESI-MS (negative): Cluster-derived peaks at m / z 1741-1875

[0112]

[0113] <Compound 3> 5 g of zirconium (IV) tetrapropoxide (70% 1-propanol solution, manufactured by Tokyo Chemical Industry Co., Ltd.), 7.32 g of cyclopentanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 11.5 mL of toluene were placed in a 100 mL recovery flask and stirred for 6 hours at 100° C. Thereafter, the mixture was cooled to 0° C. or below, and 2.3 g of precipitated compound 3 was obtained as a white solid. 1 H-NMR (CDCl3) δ 2.87-2.57 (6H, m), 2.01-1.50 (96H, m) ESI-MS (negative): Cluster-derived peaks at m / z 1700-2200

[0114]

[0115] <Preparation of Photosensitive Composition (Resist Solution)> Each of the above compounds 1 to 3 was dissolved in 2-heptanone to a concentration of 5% by mass, and the solution was filtered through a 0.2 μm filter to obtain a resist solution.

[0116] The prepared resist solution was applied to a patterned substrate (silicon wafer) by spin coating to form a resist film with a thickness of approximately 40 nm. The resulting resist film was baked at 90°C for 90 seconds, and then patterned using an electron beam lithography system (electron beam acceleration voltage: 100 keV).

[0117] <Development> After pattern writing, Compound 1 was developed with 2-methyl-2-pentanol (25°C, 30 seconds), and Compounds 2 and 3 were developed with 2-heptanone (25°C, 30 seconds) to obtain negative patterns, which were designated Examples 1 to 3, respectively.

[0118] <Measurement of Sensitivity> Extreme ultraviolet (EUV) exposure was performed while changing the irradiation dose, and the film thickness of the pattern obtained by development was measured with a contact step gauge, and the EUV irradiation dose at which the amount of change in the film thickness increased was maximized was determined as an index of sensitivity. The sensitivity was measured using the exposure dose (unit: mJ / cm ２ The results are shown in Table 1.

[0119] [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 as Comparative Example 1.

[0120] The resist solution of Comparative Example 1 was evaluated in the same manner as in Examples 1 to 3, and the results are shown in Table 1.

[0121]

[0122] From the results in Table 1, it was confirmed that, compared with Comparative Example 1, Examples 1 to 3 had a smaller EUV irradiation dose when the amount of change in film thickness was at its maximum, and therefore had higher sensitivity.

[0123] <Resolution Evaluation> The resolution of Examples 1 to 3 was evaluated using an electron beam lithography device. Line and space (line:space = 1:1) patterns with hp (half pitch) of 100 nm, 50 nm, and 30 nm were drawn, developed, and each pattern was observed under a scanning electron microscope to evaluate the drawn patterns. A rating of "A" was given when a line and space pattern was observed, a rating of "B" was given when a pattern was observed but partially crosslinked, and a rating of "C" was given when no pattern was observed. The results are shown in Table 2.

[0124]

[0125] [Results] From the results of an electron beam (EB) writing test, Examples 1 to 3 were able to form a half-pitch (hp) 100 nm, 50 nm line and space (L&S) pattern (1:1), and in particular, Examples 2 and 3 were able to form a hp 30 mm line and space (L&S) pattern (1:1). Furthermore, as shown in Table 1, it was confirmed that the samples had very high sensitivity to EUV exposure.

[0126] From the above results, it has been demonstrated that transition metal cluster compounds composed of a carboxylate ligand having an alicyclic structure of a saturated hydrocarbon and a transition metal element are relatively easy to synthesize, have high sensitivity to EUV, high throughput, are suitable for mass production, and have high resolution, making them highly practical as photoresists capable of forming ultrafine patterns.

Claims

1. A transition metal cluster compound comprising a transition metal atom and a carboxylate ligand A having an alicyclic structure of a saturated hydrocarbon.

2. The transition metal cluster compound of claim 1, wherein the carboxylate ligand A comprises a saturated hydrocarbon alicyclic structure having at least one substituent R, the substituent R being an organic group or a halogen atom.

3. The transition metal cluster compound according to claim 1, wherein the alicyclic structure of the carboxylate ligand A has 3 to 10 carbon atoms.

4. The transition metal cluster compound according to claim 1, wherein the transition metal atoms are comprised of 2 to 20 atoms.

5. The transition metal cluster compound according to claim 1, wherein the transition metal atom is titanium, hafnium, or zirconium.

6. The transition metal cluster compound according to claim 1, wherein the alicyclic structure of the carboxylate ligand A is any one of a cyclopropane ring, a cyclopentane ring, a cyclobutane ring, a cyclohexane ring, and a norbornane ring.

7. Carbon C in the alicyclic structure to which the carboxylate group of the carboxylate ligand A is bonded １ 2. The transition metal cluster compound according to claim 1, wherein is a tertiary or quaternary carbon and is one of the carbons constituting the cyclic structure of the alicyclic structure.

8. The transition metal cluster compound according to claim 2, wherein the substituent R is an organic group having 1 to 10 carbon atoms.

9. The transition metal cluster compound according to claim 2, wherein the organic group is any one of a hydrocarbon group, an aromatic group, an ester group, a sulfonyl group, an alkoxy group, an amide group, an amino group, and a carbonyl oxygen group.

10. The transition metal cluster compound according to claim 2, wherein the structure of the substituent R does not contain an unsaturated hydrocarbon or aromatic group.

11. A method for producing a transition metal cluster compound according to any one of claims 1 to 10, comprising reacting a compound containing a transition metal atom with a carboxylic acid having a carboxylate ligand A structure in a solution.

12. A photosensitive composition comprising the transition metal cluster compound according to any one of claims 1 to 10.

13. The photosensitive composition of claim 12, further comprising a solvent.

14. A photosensitive composition comprising the transition metal cluster compound according to any one of claims 1 to 10 in a concentration of 50 to 100% by mass of the total solids.

15. The photosensitive composition according to claim 12, which reacts with actinic radiation having a wavelength of 6 nm or more and 15 nm or less.

16. A pattern forming method comprising the steps of applying the photosensitive composition according to claim 12 to a substrate, exposing the photosensitive composition applied to the substrate to actinic radiation, and developing the exposed photosensitive composition.

17. The pattern formation method according to claim 16, 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.

18. A substrate having a patterned layer obtained by the patterning method according to claim 16.

19. A method for manufacturing a substrate, in which a pattern layer is formed by the pattern forming method according to claim 16.

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