Nonionic oxime compounds, organometallic compounds, acid generators, photosensitive materials for resists, and resists,

Abstract

To provide a novel nonionic oxime compound that quickly decomposes to generate an acid when exposed to ultrashort-wavelength light.SOLUTION: For example, a nonionic oxime compound represented by R1-N=C(Ar1) R2-COOH (formula 1-1) is provided, where Ar1 is an aromatic ring substituted with a halogen atom or a halogenated hydrocarbon group, R1 is -O(C=O)R group, -OS(=O)2R group, or -OPO(OR)2 group, and the R is a hydrocarbon group or a halogenated hydrocarbon group. R2 is a single bond or linking group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel nonionic oxime compound, an acid generator containing the compound, a chemically amplified resist containing the acid generator, an organometallic compound containing a ligand derived from the nonionic oxime compound, a photosensitive material for resists containing the organometallic compound, and a metal resist containing the photosensitive material for resists. [Background technology]

[0002] Nonionic oxime compounds are compounds that generate acid when irradiated with light, and are used as acid generators in chemically amplified resists.

[0003] For example, Patent Document 1 discloses that an oxime sulfonate compound represented by the following formula is highly sensitive to light with a wavelength of 365 nm and has sufficient acid generation ability even with a large film thickness.

[0004] [ka] [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-169173 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In recent years, further miniaturization, increased capacity, and performance improvements have been required for electronic devices, and this can be achieved by shortening the wavelength of the light used in photolithography.

[0007] Furthermore, the use of ultrashort wavelength light, such as extreme ultraviolet (EUV; wavelength 13.5 nm), as the aforementioned light has been considered. However, a problem has been that the oxime sulfonate compound represented by the above formula has low sensitivity to ultrashort wavelength light.

[0008] Therefore, the object of the present invention is to provide a novel nonionic oxime compound that rapidly decomposes and generates acid when irradiated with ultrashort wavelength light. Another object of the present invention is to provide an acid generator that is highly sensitive to ultrashort wavelength light. Another object of the present invention is to provide an organometallic compound suitable for use as a resist material, which forms a resist film having a high-resolution pattern and excellent etching resistance when exposed to ultrashort wavelength light. Another object of the present invention is to provide a resist material that forms a resist film having a high-resolution pattern and excellent etching resistance when exposed to ultrashort wavelength light. Another object of the present invention is to provide a resist that forms a resist film having a high-resolution pattern by exposure to ultrashort wavelength light. Another object of the present invention is to provide a resist that forms a resist film having a high-resolution pattern and excellent etching resistance when exposed to ultrashort wavelength light. [Means for solving the problem]

[0009] As a result of diligent research to solve the above problems, the present inventors have found that nonionic oxime compounds represented by the following formulas (1-1) or (1-2) are extremely sensitive to ultrashort wavelength light and have the property of rapidly decomposing and generating acid when irradiated with ultrashort wavelength light. Furthermore, it was found that the nonionic oxime compound has a carboxyl group that is coordinating to a metal or metal oxide, and when mixed with a metal or metal oxide, it forms an organometallic compound, which is an organic-inorganic composite with the metal or metal oxide as the core. It was also found that the organometallic compound has excellent photoresponsiveness and rapidly aggregates to form aggregates (or lumps) when irradiated with ultrashort wavelength light. This invention was completed based on these findings.

[0010] In other words, the present invention provides compounds represented by the following formulas (1-1) or (1-2). [ka] (In the formula, Ar 1 Ar 2 These are identical or different structures, representing an aromatic ring structure, or a structure in which two or more aromatic rings are linked by a single bond or a linking group. 1 R represents an -O(C=O)R group, an -OS(=O)2R group, or an -OPO(OR)2 group, where R represents a hydrocarbon group or a halogenated hydrocarbon group. 2 , R 5 Each of these independently represents a single bond or a linking group. 3 R represents a halogen atom or a halogenated hydrocarbon group. 4 This represents a hydrocarbon group which may have substituents, a group in which two or more hydrocarbon groups which may have substituents are bonded together by a single bond or a linking group, or a cyano group. (n1 represents an integer from 1 to 5, and n2 represents an integer from 1 to 4.)

[0011] The present invention also relates to the R 3 The present invention provides the compound wherein the compound is a fluorine atom or a trifluoromethyl group.

[0012] The present invention also provides organometallic compounds having a configuration in which the compound is coordinately bonded to a metal or metal oxide (1).

[0013] The present invention also provides the organometallic compound wherein (1) is at least one selected from hafnium, zirconium, tin, cobalt, palladium, antimony, and oxides thereof.

[0014] The present invention also provides a photosensitive material for resist containing the organometallic compound.

[0015] The present invention also provides the photosensitive material for resist which is a photosensitive material for extreme ultraviolet rays or electron beams.

Effects of the Invention

[0016] Since the nonionic oxime type compound of the present invention contains a halogen atom or a halogenated hydrocarbon group, it has good sensitivity to light rays of an ultrashort wavelength. When irradiated with light rays of an ultrashort wavelength, it decomposes rapidly to generate an acid (HR 1 ; R 1 corresponds to R in formula (1-1) or (1-2) 1 ). Further, since the nonionic oxime type compound has excellent solvent solubility, it is uniformly dispersed in the resist. Furthermore, since the nonionic oxime type compound contains a carboxylic acid group, it has excellent developability and has an effect of reducing development residues. Therefore, if a chemically amplified resist containing the nonionic oxime type compound and a photosensitive resin is irradiated with light rays of an ultrashort wavelength, a fine pattern can be accurately transferred, and a resist film having a high-resolution fine pattern can be manufactured.

[0017] Furthermore, because the nonionic oxime compound contains a carboxylic acid group, it exhibits coordination properties with metals or metal oxides. The organometallic compound formed by the coordination bonding of the nonionic oxime compound to a metal or metal oxide exhibits good solubility in solvents. Moreover, the organometallic compound has excellent photoresponsiveness; when irradiated with light, it efficiently senses even ultrashort wavelength light and forms aggregates. These organometallic compound aggregates no longer exhibit solubility in solvents. In addition, because the aggregates have a structure composed of aggregated metals or metal oxides, they possess toughness that allows them to withstand etching. Therefore, if a layer containing the organometallic compound in a highly dispersed state is thinned to a thickness that allows ultrashort wavelength light to reach the bottom, and then exposed to a pattern shape using ultrashort wavelength light, followed by washing with a solvent, the organometallic compound in the unexposed areas will be washed away, but the organometallic compound in the exposed areas will aggregate and remain without being washed away, thus enabling the precise manufacture of a resist film with a high-resolution fine pattern. Furthermore, the resist film obtained in this way possesses etching resistance even when thin.

[0018] Furthermore, by using the above-mentioned resist film to perform etching on the substrate (for example, dry etching using a reactive gas or plasma), semiconductor devices with high-resolution patterns (for example, wiring patterns, circuit patterns, etc.) can be manufactured with a high yield. [Modes for carrying out the invention]

[0019] [Nonionic oxime compounds] The nonionic oxime compound of the present invention is a compound represented by the following formula (1-1) or (1-2). [ka] (In the formula, Ar 1 Ar 2 These are identical or different structures, representing an aromatic ring structure, or a structure in which two or more aromatic rings are linked by a single bond or a linking group. 1R represents an -O(C=O)R group, an -OS(=O)2R group, or an -OPO(OR)2 group, where R represents a hydrocarbon group or a halogenated hydrocarbon group. 2 , R 5 Each of these independently represents a single bond or a linking group. 3 R represents a halogen atom or a halogenated hydrocarbon group. 4 This represents a hydrocarbon group which may have substituents, a group in which two or more hydrocarbon groups which may have substituents are bonded together by a single bond or a linking group, or a cyano group. (n1 represents an integer from 1 to 5, and n2 represents an integer from 1 to 4.)

[0020] The aforementioned Ar 1 Ar 2 Examples of aromatic ring structures in this context include aromatic hydrocarbon rings with 6 to 15 carbon atoms, such as benzene rings, naphthalene rings, and anthracene rings.

[0021] The aforementioned Ar 1 Ar 2 Examples of structures in which two or more aromatic rings are linked by single bonds or linking groups include structures in which two or more aromatic hydrocarbon rings are linked by single bonds, ether bonds (-O-), or thioether bonds (-S-).

[0022] The aforementioned Ar 1 Ar 2 From the viewpoint of increasing sensitivity to ultrashort wavelength light, it is preferable that the structure be a benzene ring structure or a structure in which two or more benzene rings are linked by a single bond or a linking group (preferably an ether bond or a thioether bond), and at least one structure selected from the benzene ring structure and the structures represented by the following formulas (ar-1) to (ar-3) is particularly preferred. [ka]

[0023] The aforementioned R 1The hydrocarbon groups (=monovalent hydrocarbon groups) in R include monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and monovalent groups formed by the combination of these.

[0024] Examples of the aliphatic hydrocarbon group include linear or branched alkyl groups having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, and pentyl groups; linear or branched alkenyl groups having 2 to 5 carbon atoms (preferably 2 to 3 carbon atoms), such as vinyl, allyl, and 1-butenyl groups; and alkynyl groups having 2 to 5 carbon atoms (preferably 2 to 3 carbon atoms), such as ethynyl and propynyl groups.

[0025] Examples of the alicyclic hydrocarbon group include cycloalkyl groups with 3 to 10 members (preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; cycloalkenyl groups with 3 to 10 members (preferably 5 to 8 members) such as cyclopentenyl and cyclohexenyl groups; perhydronaphthalene-1-yl, norbornyl, adamantyl, and tricyclo[5.2.1.0 2,6 ] Decane-8-yl group, tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include bridged cyclic hydrocarbon groups such as dodecane-3-yl groups.

[0026] Examples of the aforementioned aromatic hydrocarbon group include C such as a phenyl group and a naphthyl group. 6-10 An example is the aryl group.

[0027] The aforementioned R 1 Examples of halogenated hydrocarbon groups in R include groups in which at least one hydrogen atom of the monovalent hydrocarbon group is substituted with a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, iodine, and astatine. From the viewpoint of increasing resist sensitivity, the halogen atom is preferably fluorine or iodine, and particularly preferably fluorine.

[0028] Among the halogenated hydrocarbon groups, a group in which all of the hydrogen atoms of the monovalent hydrocarbon group are replaced by halogen atoms (i.e., a perhalogenated hydrocarbon group) is preferred. Furthermore, the number of carbon atoms in the halogenated hydrocarbon group is, for example, 1 to 10, preferably 1 to 6.

[0029] The halogenated hydrocarbon group is preferably a haloalkyl group or a haloaryl group, and particularly preferably a haloC 1-5 Alkyl or halo C 6-10 It is an aryl group.

[0030] The halogenated hydrocarbon group is preferably a perhaloalkyl group or a perhaloaryl group, and particularly preferably a perhalo C 1-5 Alkyl or perhalo C 6-10 It is an aryl group.

[0031] The aforementioned R 1 The R group is preferably a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent halogenated aliphatic hydrocarbon group, or a monovalent halogenated aromatic hydrocarbon group, and is particularly preferably an alkyl group, an aryl group, a halogenated alkyl group (=haloalkyl group), or a halogenated aryl group (=haloaryl group).

[0032] The aforementioned R 2 , R 5 Each of these independently represents a single bond or a linking group. The linking group is a divalent group having one or more atoms, and examples include a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), an amide bond (-CONH-), a carbonate bond (-OCOO-), and a group formed by linking multiple such bonds.

[0033] Examples of the divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 5 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene; cycloalkylene groups having 3 to 18 carbon atoms, such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene; and arylene groups having 6 to 14 carbon atoms, such as o-phenylene, m-phenylene, p-phenylene, and naphthylene.

[0034] Examples of the aforementioned divalent halogenated hydrocarbon group include a group in which at least one of the hydrogen atoms of the divalent hydrocarbon group is substituted with a halogen atom.

[0035] The aforementioned R 2 Preferably, the group is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group, or a divalent group in which two or more of these groups are linked via an ether bond or a thioether bond.

[0036] The aforementioned R 2 From the viewpoint of improving solvent solubility, alkylene groups, halogenated alkylene groups, or divalent groups in which two or more of these groups are linked via ether bonds or thioether bonds are preferred.

[0037] The aforementioned R 5 From the viewpoint of improving solvent solubility and thermal stability, divalent hydrocarbon groups, divalent halogenated hydrocarbon groups, or divalent groups formed by bonding these groups with ether bonds or thioether bonds, or single bonds are preferred.

[0038] The aforementioned R 5 Among these, alkylene groups, halogenated alkylene groups, or divalent groups formed by bonding these groups with ether bonds or thioether bonds, or single bonds are preferred.

[0039] The aforementioned R 3 is Ar 1The substituent bonded to the atom represents a halogen atom or a halogenated hydrocarbon group. Examples of halogen atoms include fluorine, chlorine, bromine, iodine, and astatine. From the viewpoint of increasing sensitivity to ultrashort wavelength light, the halogen atom is preferably fluorine or iodine, and particularly preferably fluorine.

[0040] The halogenated hydrocarbon group is R 1 Similar examples can be given to the halogenated hydrocarbon group in R. Among the halogenated hydrocarbon groups, perhalogenated hydrocarbon groups are preferred. Furthermore, the number of carbon atoms in the halogenated hydrocarbon group is, for example, 1 to 5, preferably 1 to 3, and particularly preferably 1 or 2.

[0041] The halogenated hydrocarbon group is preferably a haloalkyl group, and particularly preferably C 1-5 It is a haloalkyl group.

[0042] The halogenated hydrocarbon group is preferably a perhaloalkyl group, and particularly preferably C 1-5 It is a perhaloalkyl group.

[0043] n1 is the aforementioned Ar 1 R that joins 3 This indicates a number, which is an integer between 1 and 5. Among these, an integer between 1 and 3 is preferred, and 1 or 2 is particularly preferred.

[0044] n2 is the aforementioned Ar 2 R that joins 3 This represents a number, which is an integer between 1 and 4.

[0045] The aforementioned Ar 1 R 3 It may also have other substituents. 2 R 3 R shown in equation (1-2) 5The group may have other substituents besides the -COOH group. Examples of other substituents include monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups, oxo groups, carboxyl groups, and groups represented by the following formula (r). -X 1 -R (r) (In formula (r), X 1 represents -O-, -S-, or -CO-, and R represents a hydrocarbon group or a halogenated hydrocarbon group. The bond emanating from the left end of formula (r) is the Ar 1 Ar 2 (Bonds to carbon atoms that make up the aromatic ring structure in the fragrance ring.)

[0046] The hydrocarbon group and halogenated hydrocarbon group in R in the above formula (r) are as follows: 1 Similar examples can be given to halogenated hydrocarbon groups in the R component.

[0047] In formula (r), R is preferably a monovalent aliphatic hydrocarbon group or a monovalent halogenated aliphatic hydrocarbon group, and more preferably an alkyl group or a haloalkyl group, and especially C 1-5 Alkyl or halo C 1-5 Alkyl alkyl groups are preferred.

[0048] The aforementioned R 4 This represents a hydrocarbon group which may have substituents, a group in which two or more hydrocarbon groups which may have substituents are bonded together by a single bond or a linking group, or a cyano group.

[0049] The aforementioned R 4 The hydrocarbon group (= monovalent hydrocarbon group) in is the aforementioned R 1 Similar examples can be given to the monovalent hydrocarbon group in R. 2 , R 5 Similar examples can be given to the linking group in [the relevant context].

[0050] The aforementioned R 4The hydrocarbon group in is preferably a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group, and among these, alkyl groups or aryl groups are particularly preferred, especially C 1-5 Alkyl alkyl group or C 6-10 An aryl group is preferred.

[0051] The aforementioned R 4 As for the hydrocarbon group in this, from the viewpoint of increasing solvent solubility, a monovalent aliphatic hydrocarbon group is preferred, and an alkyl group is particularly preferred, especially C 1-5 Alkyl alkyl groups are preferred.

[0052] Furthermore, the R 4 In the above, a group in which two or more hydrocarbon groups are bonded via a linking group is preferably a monovalent group in which two or more hydrocarbon groups are bonded via an ether bond or a thioether bond.

[0053] The aforementioned R 4 Examples of substituents that the hydrocarbon group may have include halogen atoms.

[0054] As the nonionic oxime compound, compounds represented by the following formulas (1-1-1) or (1-2-1) are preferred. [ka]

[0055] In the above formula, R 1 , R 2 , R 3 , R 4 n1 and n2 are the same as above.

[0056] If n1 is an integer less than or equal to 4, the benzene ring shown in equation (1-1-1) is R 3 It may have other substituents. Also, if n2 is an integer less than or equal to 3, the benzene ring shown in formula (1-2-1) is R 3 and R 5The group may have other substituents besides the -COOH group. Examples of other substituents include groups selected from hydrocarbon groups, oxy hydrocarbon groups, and thio hydrocarbon groups.

[0057] The oxy hydrocarbon group is a group represented as [-OR; R is a hydrocarbon group] such as a methoxy group, ethoxy group, butoxy group, t-butoxy group, etc., and the hydrocarbon group in R is the above R 1 Similar examples can be given to the monovalent hydrocarbon group in R. The number of carbon atoms in the oxy hydrocarbon group is, for example, 1 to 5, preferably 1 to 3, and particularly preferably 1 or 2.

[0058] The thiohydrocarbon group is a group represented by [-SR; R is a hydrocarbon group] such as a methylthio group, an ethylthio group, or a butylthio group, and the hydrocarbon group in R is the above R 1 Similar examples can be given for the monovalent hydrocarbon group in R. The number of carbon atoms in the thiohydrocarbon group is, for example, 1 to 5, preferably 1 to 3, and particularly preferably 1 or 2.

[0059] [Acid Generator] The acid generator of the present invention comprises one or more of the nonionic oxime type compounds.

[0060] The acid generator may contain other components besides the nonionic oxime compound, but the proportion of the nonionic oxime compound in the total amount of compounds in the acid generator that decompose upon light irradiation to generate acid is, for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably 99% by weight or more, and especially preferably 99.9% by weight or more. The upper limit is 100% by weight.

[0061] The acid generator (or the nonionic oxime compound) has excellent solubility in a solvent (e.g., PGMEA), and the amount of the acid generator (or the nonionic oxime compound) that dissolves in 100 parts by weight of PGMEA at room temperature and pressure is, for example, more than 2 parts by weight, preferably 3 parts by weight or more, more preferably 4 parts by weight or more, particularly preferably 5 parts by weight or more, most preferably 8 parts by weight or more, and especially preferably 15 parts by weight or more. The upper limit is, for example, 30 parts by weight.

[0062] Furthermore, the acid generator exhibits excellent sensitivity to ultrashort wavelength light, and when irradiated with such light, it quickly generates acid (HR 1 ;R 1 R in equation (1-1) or (1-2) 1 This generates (corresponding to). The wavelength of the light is, for example, 100 nm or less (for example, 1 to 100 nm), preferably 80 nm or less, particularly preferably 50 nm or less, most preferably 30 nm or less, and especially preferably 20 nm or less. The light includes, for example, X-rays, electron beams, EUV, etc.

[0063] The acid generator possesses thermal stability, and decomposition can be suppressed even when subjected to heat treatment (for example, heating at a temperature of 50°C or higher but less than 100°C for 1 to 5 minutes). Therefore, the coating film containing the acid generator can be heat-dried while maintaining its acid-generating ability, resulting in excellent workability.

[0064] Because the acid generator has the above-mentioned properties, it can be suitably used as an acid generator for photoresists (e.g., chemically amplified resists) that use ultrashort wavelength light such as extreme ultraviolet light or electron beams.

[0065] [Chemically Amplified Resist] The chemically amplified resist of the present invention comprises the acid generator (or the nonionic oxime compound) and a photosensitive resin. The acid generator and the photosensitive resin may each be contained individually or in combination of two or more types.

[0066] The content of the acid generator (or the nonionic oxime compound) is, for example, 0.001 to 20% by weight, preferably 0.01 to 15% by weight, and particularly preferably 0.05 to 7% by weight, based on the total amount of the photosensitive resin.

[0067] If the content of the acid generator (or the nonionic oxime compound) is 0.001% by weight or more, excellent photosensitivity to ultrashort wavelength light such as X-rays and EUV can be achieved. Furthermore, if the content is 20% by weight or less, the effect of improving the resolution of the photoresist can be obtained.

[0068] The aforementioned photosensitive resins include negative-type photosensitive resins (QN) whose solubility decreases upon light irradiation (or unexposed areas are removed), and positive-type photosensitive resins (QP) whose solubility increases upon light irradiation (or exposed areas are selectively removed). These can be selected and used according to the application.

[0069] A negative-type photosensitive resin (or negative-type chemically amplified resin; QN) is, for example, a composition containing one phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2), either individually or in combination of two or more.

[0070] The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a resin containing phenolic hydroxyl groups. Examples include novolac resin, polyhydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic acid derivatives, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing phenolic hydroxyl groups, polyamic acid containing phenolic hydroxyl groups, and phenol-dicyclopentadiene condensation resin.

[0071] The phenolic hydroxyl group-containing resin (QN1) may contain phenolic low-molecular-weight compounds as part of its components.

[0072] The polystyrene-equivalent weight-average molecular weight (Mw) of phenolic hydroxyl group-containing resin (QN1), as measured by GPC, is, for example, 2000 to 20000.

[0073] The crosslinking agent (QN2) can be any compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with the acid generated from the acid generator. Examples include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, novolac resin epoxy compounds, resol resin epoxy compounds, poly(hydroxystyrene) epoxy compounds, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenol compounds, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group-containing urea resins, carboxymethyl group-containing phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, and carboxymethyl group-containing phenol compounds. These can be used individually or in combination of two or more.

[0074] From the viewpoint of forming patterns with high precision, the content of the crosslinking agent (QN2) is, for example, 10 to 40 mol% relative to the total acidic functional groups in the phenolic hydroxyl group-containing resin (QN1).

[0075] Positive-type photosensitive resins (or positive-type chemically amplified resins; QP) include alkali-soluble resins (protective group-introduced resins; QP1) into which acid-dissociable groups are introduced as protecting groups.

[0076] Protecting group-introduced resins (QP1) are resins in which some or all of the hydrogen atoms of acidic functional groups (e.g., phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, etc.) in an alkali-soluble resin are replaced with acid-dissociable groups.

[0077] The protective group-introducing resin (QP1) itself is an alkali-insoluble or alkali-slightly alkali-soluble resin. When the acid-dissociable groups are dissociated by the strong acid generated from the acid generator, an alkali-soluble resin that readily dissolves in an alkaline developer is produced.

[0078] The alkali-soluble resin is, for example, a resin with an HLB value of 4 to 19 (preferably 5 to 18, particularly preferably 6 to 17).

[0079] Alkali-soluble resins include resins containing phenolic hydroxyl groups, resins containing carboxyl groups, and resins containing sulfonic acid groups.

[0080] Examples of phenolic hydroxyl group-containing resins include resins similar to the phenolic hydroxyl group-containing resin (QN1) described above.

[0081] The carboxyl group-containing resin is not particularly limited as long as it is a polymer having carboxyl groups. Examples include homopolymers of carboxyl group-containing vinyl monomers (Ba) and homopolymers of carboxyl group-containing vinyl monomers (Ba) and hydrophobic group-containing vinyl monomers (Bb).

[0082] An example of a carboxyl group-containing vinyl monomer (Ba) is (meth)acrylic acid.

[0083] Examples of hydrophobic group-containing vinyl monomers (Bb) include C 1-20 Examples include (meth)acrylic acid esters (Bb1) such as alkyl (meth)acrylates and alicyclic group-containing (meth)acrylates, and aromatic hydrocarbon monomers (Bb2) such as hydrocarbon monomers having a styrene skeleton and vinylnaphthalene.

[0084] The sulfonic acid group-containing resin is not particularly limited as long as it is a polymer having sulfonic acid groups. For example, it can be obtained by vinyl polymerization of a sulfonic acid group-containing vinyl monomer (Bc), such as vinyl sulfonic acid or styrene sulfonic acid, and, if necessary, a hydrophobic group-containing vinyl monomer (Bb).

[0085] Examples of acid-dissociable groups in the protecting group-introducing resin (QP1) include 1-substituted methyl groups such as methoxymethyl, benzyl, and tert-butoxycarbonylmethyl groups; 1-substituted ethyl groups such as 1-methoxyethyl and 1-ethoxyethyl groups; 1-branched alkyl groups such as tert-butyl groups; silyl groups such as trimethylsilyl groups; gelmyl groups such as trimethylgermyl groups; alkoxycarbonyl groups such as tert-butoxycarbonyl groups; acyl groups; and cyclic acid-dissociable groups such as tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, and tetrahydrothiofuranyl groups. These may be present individually or in combination of two or more.

[0086] The rate of introduction of acid-dissociable groups in the protecting group-introduced resin (QP1) {the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protecting group-introduced resin (QP1)} cannot be defined in general terms depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but it is preferably 10 to 100%, and more preferably 15 to 100%.

[0087] The polystyrene-equivalent weight-average molecular weight (Mw) of the protective group-introduced resin (QP1), as measured by GPC, is, for example, 1,000 to 150,000, preferably 3,000 to 100,000.

[0088] The chemically amplified resist of the present invention can be prepared, for example, by dissolving the acid generator (or the nonionic oxime compound) in an organic solvent and mixing it with a photosensitive resin.

[0089] The chemically amplified resist of the present invention may contain one or more other components as needed, in addition to the acid generator (or the nonionic oxime compound) and the photosensitive resin. Examples of other components include organic solvents, pigments, dyes, photosensitizers, dispersants, surfactants, fillers, leveling agents, defoamers, antistatic agents, ultraviolet absorbers, pH adjusters, surface modifiers, plasticizers, drying accelerators, and the like.

[0090] The organic solvent can be any solvent that can dissolve the photosensitive resin and impart good coatability to the photoresist, but it is preferable to use one with a boiling point of 200°C or lower, as this allows for easy drying after application of the photoresist. Preferred organic solvents include aromatic hydrocarbons such as toluene; alcohols such as ethanol and methanol; ketones such as cyclohexanone, methyl ethyl ketone, and acetone; esters such as ethyl acetate, butyl acetate, and ethyl lactate; and glycol monoether monoesters such as propylene glycol monomethyl ether acetate (PGMEA). These can be used individually or in combination of two or more.

[0091] The chemically amplified resist of the present invention contains a nonionic oxime compound that has high photosensitivity to ultrashort wavelength light such as X-rays, electron beams, and EUV. Therefore, by using the chemically amplified resist of the present invention, a resist film with a high resolution and fine pattern can be manufactured by photolithography using ultrashort wavelength light.

[0092] [Organometallic compound] The organometallic compounds of the present invention are compounds having a structure in which a compound represented by the above formula (1-1) or (1-2) is coordinately bonded to a metal or metal oxide (1).

[0093] The organometallic compound of the present invention comprises a metal or metal oxide (1) and a ligand derived from the compound represented by the above formula (1-1) or (1-2).

[0094] The organometallic compound of the present invention is an organic-inorganic composite obtained by reacting a metal or metal oxide (1) with a complexing agent (2), and the complexing agent (2) contains at least a compound represented by the above formula (1-1) or (1-2).

[0095] The organometallic compound may contain components other than the ligands derived from the metal or metal oxide (1) and the complexing agent (2). However, in the total amount (100% by weight) of the organometallic compound, the proportion of the total weight of the ligands derived from the metal or metal oxide (1) and the complexing agent (2) is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more, and particularly preferably 99% by weight or more. The upper limit is 100% by weight.

[0096] The organometallic compound has excellent solubility (or dispersibility) in a solvent, and the average particle diameter (particle diameter determined by the dynamic light scattering method) in a solvent (e.g., PGMEA) is, for example, 200 nm or less, preferably 100 nm or less, particularly preferably 50 nm or less. The lower limit is, for example, 1 nm.

[0097] The organometallic compound has excellent sensitivity to light. When irradiated with light, an acid (HR 1 ; R 1 corresponds to R in formula (1-1) or (1-2) 1 ) is generated and it aggregates rapidly. The wavelength of the light is, for example, 100 nm or less (e.g., 0 to 100 nm), preferably 80 nm or less, particularly preferably 50 nm or less, most preferably 30 nm or less, and particularly preferably 20 nm or less. The light includes, for example, X-rays, electron beams (EB), EUV, etc. The organometallic compound can be produced, for example, by mixing a metal or metal oxide (1) and a complexing agent (2) containing at least a compound represented by the above formula (1-1) or (1-2) in a solvent.

[0098] The amount of complexing agent (2) used is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 1 part by weight of the above-mentioned metal or metal oxide (1).

[0099] The amount of the compound represented by formula (1-1) or (1-2) used (the total amount when using both the compound represented by formula (1-1) and the compound represented by formula (1-2)) is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 1 part by weight of the metal or metal oxide (1).

[0100] Examples of the aforementioned solvents include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether, propylene glycol methyl ether, and propylene glycol monomethyl ether acetate. These can be used individually or in combination of two or more.

[0101] The amount of solvent used is, for example, about 50 to 300% by weight relative to the total amount of metal or metal oxide (1) and complexing agent (2).

[0102] After this reaction is complete, the resulting reaction product can be separated and purified by general precipitation, washing, and filtration procedures.

[0103] (Metal or metal oxide (1)) The metal or metal oxide (1) is a component that forms the core of the organometallic compound and includes at least one selected from metals and metal oxides.

[0104] Examples of the aforementioned metals include hafnium, zirconium, tin, cobalt, palladium, antimony, titanium, and aluminum.

[0105] The aforementioned metal oxides include oxides of the metal and their partial hydroxides (or hydrates). Examples of the aforementioned metal oxides include hafnium oxide (HfO2), zirconium oxide (ZrO2, Zr6O4(OH)4), and tin oxide (SnO2, Sn2O3, Sn3O4, Sn6O4). 12 Sn 12 O 25 H 16 (C4H9Sn) 12 O 14 Examples include (OH)6), cobalt oxide (CoO, Co2O3, Co3O4), palladium oxide (PdO), antimony oxide (Sb2O3), titanium oxide (TiO2), and aluminum oxide (Al2O3).

[0106] The aforementioned metal oxide can be produced, for example, by the sol-gel method. Specifically, a metal alkoxide is used as a starting material, and the metal oxide is ultimately obtained through hydrolysis, polycondensation, and a sol / gel state.

[0107] There are no particular restrictions on the shape of the metal or metal oxide (1), and examples include spherical (perfectly spherical, nearly spherical, ellipsoidal, etc.), polyhedral, rod-shaped (cylindrical, prismatic, etc.), plate-shaped, flake-shaped, and irregularly shaped. Furthermore, the metal or metal oxide (1) may be hollow, porous, or solid.

[0108] The average particle size of the metal or metal oxide (1) (particle size determined by dynamic light scattering) is, for example, 1 to 200 nm, preferably 2 to 100 nm, and particularly preferably 2 to 50 nm.

[0109] In the total amount of the organometallic compound (or the total weight of the metal or metal oxide (1) and the ligand derived from the compound represented by the formula (1-1) or (1-2) above), the proportion of the metal or metal oxide (1) is, for example, 10 to 90% by weight, preferably 30 to 70% by weight.

[0110] (Complexing agent (2)) The complexing agent (2) contains a compound represented by the above formula (1-1) or (1-2), and may also have one or more other complexing agents.

[0111] Examples of other complexing agents include carboxylic acids, phosphoric acids, phosphonic acids, and sulfonic acids.

[0112] Examples of the carboxylic acid include C alkyl carboxylic acids such as citric acid, oxalic acid, malic acid, maleic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, succinic acid, malonic acid, fumaric acid, phthalic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, glycolic acid, glyceric acid, lactic acid, etc.; 1-10 C alkenyl carboxylic acids such as acrylic acid, methacrylic acid, tiglic acid, 2-methylisocrotonic acid, 3-methylcrotonic acid, etc.; 2-10 C aryl carboxylic acids such as benzoic acid, salicylic acid, crotonic acid, etc. 6-10 are included.

[0113] Examples of the phosphoric acid include C alkyl phosphoric acids such as methyl phosphate, ethyl phosphate, propyl phosphate, butyl phosphate, hexyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate; 1-10 C aryl phosphoric acids such as diphenyl phosphate, etc. 6-10 are included.

[0114] Examples of the phosphonic acid include C alkyl phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, hexylphosphonic acid, etc.; 1-10 C alkenyl phosphonic acids such as vinylphosphonic acid, etc.; 2-10 C aryl phosphonic acids such as phenylphosphonic acid, etc. <00%0104>are included.

[0115] Examples of the aforementioned sulfonic acid include methylsulfonic acid, ethylsulfonic acid, propylsulfonic acid, butylsulfonic acid, hexylsulfonic acid, etc. 1-10 Alkyl sulfonic acid; C such as phenyl sulfonic acid 6-10 Aryl sulfonic acid; vinyl sulfonic acid, etc. 2-10 Alkenyl sulfonic acid is one example.

[0116] Among other complexing agents, C is particularly noteworthy for its ability to impart good dispersibility to organometallic compounds. 6-10 Preferably, a carboxylic acid, phosphoric acid, phosphonic acid, or sulfonic acid having an aryl group is used, and especially C 6-10 Arylcarboxylate salts are preferred.

[0117] When the complexing agent (2) contains a compound represented by formula (1-1) or (1-2) along with other complexing agents, the proportion of the compound represented by formula (1-1) or (1-2) in the total amount of the complexing agent (2) (the total proportion if it contains both the compound represented by formula (1-1) and the compound represented by formula (1-2)) is, for example, 0.1% by weight or more, preferably 0.5% by weight or more, and particularly preferably 1.0% by weight or more. The upper limit is, for example, 50% by weight, preferably 30% by weight.

[0118] In the total amount of the organometallic compound (or the total weight of the metal or metal oxide (1) and the ligand), the proportion of ligands derived from the compound represented by formula (1-1) or (1-2) (the total proportion if it includes ligands derived from the compound represented by formula (1-1) and ligands derived from the compound represented by formula (1-2)) is, for example, 0.1 to 50% by weight, preferably 0.5 to 30% by weight.

[0119] Furthermore, the content of ligands derived from the compound represented by formula (1-1) or (1-2) above (the total content if it includes ligands derived from the compound represented by formula (1-1) and ligands derived from the compound represented by formula (1-2) above) is, for example, 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight, per 100 parts by weight of metal or metal oxide (1).

[0120] The aforementioned organometallic compound aggregates when irradiated with light. The aggregation mechanism is thought to be as follows: Although the metal or metal oxide (1) is a fine particle and has a tendency to aggregate, the organometallic compound has compounds represented by formula (1-1) or (1-2) bound to the surface of the metal or metal oxide (1), thereby suppressing aggregation between the metal or metal oxide (1) particles and achieving dispersibility. When irradiated with light, it is thought that the number of bound ligands decreases through the reactions 1, 2, and 3 below, resulting in a loss of dispersibility and the formation of aggregates. 1. A portion of the compound represented by formula (1-1) or (1-2) decomposes into an acid (HR 1 ) will occur. 2. The acid generated (HR 1 ) reacts with the organometallic compound, causing the ligand bonded to the surface of the metal oxide (1) to be detached. 3. A metal or metal oxide (1) loses its dispersibility due to a decrease in the number of ligands bonded to its surface.

[0121] The following shows the aggregation reaction of organometallic compounds when the compound represented by formula (1-1) is used as the complexing agent (2). In the following formula, M represents a metal or metal oxide (1). In the following formula, R a The dashed line indicates the part of the ligand that forms a coordinate bond with M in the following formula (= ligand derived from the compound represented by formula (1-1) above). [ka]

[0122] [Photosensitive material for resists] The aforementioned photosensitive material for resists (for example, photosensitive material for photoresists) is a photosensitive material used in the field of photolithography (for example, a compound whose solubility in a solvent changes upon irradiation with light), and includes the organometallic compounds mentioned above.

[0123] The photosensitive material for photoresist may contain other components besides the organometallic compounds described above, but the proportion of the organometallic compounds in the total amount of the photosensitive material for photoresist is, for example, 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably 99% by weight or more, and especially preferably 99.9% by weight or more. The upper limit is 100% by weight.

[0124] The photosensitive material for photoresist exhibits excellent solubility (or dispersibility) in solvents (e.g., PGMEA). The average particle size (particle size determined by dynamic light scattering) of the photosensitive material for photoresist in the solvent is, for example, 200 nm or less, preferably 100 nm or less, and particularly preferably 50 nm or less. The lower limit is, for example, 1 nm.

[0125] Furthermore, the photosensitive material for resist exhibits excellent sensitivity to ultrashort wavelength light, and upon irradiation with such light, it quickly forms aggregates. The wavelength of the light is, for example, 100 nm or less, preferably 80 nm or less, and particularly preferably 50 nm or less. The light includes, for example, X-rays, electron beams (EB), EUV, etc.

[0126] The photosensitive resist material possesses thermal stability, and aggregation is suppressed even when subjected to heat treatment (for example, heating at a temperature of 50°C to less than 130°C for 1 to 5 minutes). Therefore, the coating film containing the photosensitive resist material can be heat-dried while suppressing aggregation, resulting in excellent workability.

[0127] Because the aforementioned photosensitive material for resists has the above-described characteristics, it can be suitably used as a photosensitive material for negative-type resists. It can also be suitably used as a photosensitive material for photoresists (e.g., metal resists) that use ultrashort wavelength light such as extreme ultraviolet light or electron beams.

[0128] [Metal Resist] The metal resist of the present invention is a resist used in the field of photolithography for forming a patterned resist film, and comprises the above-mentioned organometallic compound and a solvent, wherein the organometallic compound is contained in the solvent in a dissolved (or highly dispersed) state.

[0129] In the resist, the organometallic compound is contained in a stably dissolved (or highly dispersed) state. The average particle size of the organometallic compound in the resist (particle size determined by dynamic light scattering) is, for example, 200 nm or less, preferably 100 nm or less, and particularly preferably 50 nm or less. The lower limit is, for example, 1 nm. Therefore, by using the resist, a resist film with a low LER and high resolution fine pattern can be obtained.

[0130] Examples of the aforementioned solvents include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; and (poly)C such as ethylene glycol monoacetate, diethylene glycol monoacetate, diethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, and dipropylene glycol monoacetate. 1-5 Alkylene glycol esters; (poly)C such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol n-propyl ether, propylene glycol phenyl ether, tripropylene glycol methyl-n-propyl ether, etc. 1-5 Alkylene glycol ethers; (poly)C such as ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), etc. 1-5Examples include alkylene glycol ether esters; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic hydrocarbons such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; and dimethyl sulfoxide. These can be used individually or in combination of two or more.

[0131] The content of the organometallic compound is, for example, 0.5 to 50% by weight, preferably 1.0 to 30% by weight, of the total amount of the resist (100% by weight).

[0132] The solvent content is, for example, 50 to 99.5% by weight, preferably 70 to 99% by weight, of the total amount of the resist (100% by weight).

[0133] The resist may contain other components besides the organometallic compound and solvent, such as leveling agents and quenchers.

[0134] In the total amount of the resist (100% by weight), the proportion of the total weight of the organometallic compound and the solvent is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more, and especially preferably 99% by weight or more. The upper limit is 100% by weight.

[0135] The resist contains at least the organometallic compound as nonvolatile content. The proportion of the organometallic compound in the total amount of nonvolatile content (100% by weight) is, for example, 60% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, most preferably 95% by weight or more, and especially preferably 99% by weight or more. The upper limit is 100% by weight.

[0136] In this specification, the non-volatile components of the resist refer to the components containing the organometallic compound, for example, the components remaining after heating the resist at 100°C for 1 hour under normal pressure.

[0137] Furthermore, the resist is irradiated with light (the integrated light intensity is, for example, 5 to 500 mJ / cm²). 2 If this occurs, the organometallic compounds contained in the resist will quickly form aggregates. Furthermore, from the viewpoint of further refining the pattern, it is preferable to shorten the wavelength of the light, for example, 100 nm or less (for example, 1 to 100 nm) is preferred, 80 nm or less is more preferred, 50 nm or less is particularly preferred, 30 nm or less is most preferred, and 20 nm or less is especially preferred. The light includes, for example, X-rays, electron beams (EB), EUV, etc.

[0138] Because the resist has the above-described characteristics, it can be suitably used as a negative-type resist. It can also be suitably used as a resist for photolithography using ultrashort wavelength light such as extreme ultraviolet light or electron beams.

[0139] [Manufacturing methods for electronic devices] By using the aforementioned chemically amplified resist or metal resist, a resist film with a fine pattern that is highly accurate and has excellent etching resistance can be formed, for example, through the following steps 1 to 3.

[0140] Step 1: A step of applying the resist onto a substrate and drying it to form a coating film. Step 2: A step of transferring a pattern by irradiating the coating film with light. Step 3: Development process

[0141] (Process 1) This process involves applying the resist onto the substrate to be etched and drying it to form an organometallic compound layer. Through this process, a [substrate / organometallic compound layer] laminate is obtained.

[0142] For coating the resist, known methods such as spin coating, curtain coating, roll coating, spray coating, and screen printing can be used.

[0143] The substrate on which the resist is coated may be subjected to surface treatment as needed. For example, an adhesion agent such as hexamethyldisilazane (HMDS) may be applied to the surface of the substrate to improve the adhesion of the resist film.

[0144] There are no particular restrictions on the method of drying the resist coating film, but when using the metal resist, the organometallic compounds contained therein have thermal stability, so it can also be dried by heating (for example, heating at a temperature of 50°C or higher but less than 130°C for 1 to 5 minutes), which offers excellent workability.

[0145] The thickness of the coating film is, for example, 1000 nm or less, preferably 100 nm or less. The lower limit of the thickness is, for example, 1 nm. When the metal resist is used, the aggregate of the organometallic compound contains metal or metal oxide and therefore possesses toughness. As a result, even if the coating film thickness is thinned to the extent that the irradiated light can reach the bottom surface, a resist film with excellent etching resistance can be formed.

[0146] (Process 2) This step involves transferring a pattern to the organometallic compound layer obtained in step 1 by irradiating it with light, for example, by irradiating it with light through a photomask having a pattern.

[0147] When light is irradiated through a photomask having a pattern, if the chemically amplified resist is used, the acid generator contained therein rapidly decomposes to generate acid, changing the solubility of the photosensitive resin in the developer. On the other hand, if the metal resist is used, the organometallic compounds in the exposed areas aggregate and adhere to the substrate, while the organometallic compounds in the unexposed areas do not aggregate and maintain their solubility.

[0148] While there are no particular restrictions on the light beam used for irradiation, as long as it can initiate the aggregation of organometallic compounds contained in the coating film, using an ultrashort wavelength light source such as EUV or electron beams is preferable because it allows for the precise transfer of extremely fine patterns.

[0149] When using the aforementioned metal resist, as described above, the coating can be thinned while maintaining etching resistance. By thinning the film, light rays can reach the bottom of the coating, allowing for the formation of a highly accurate pattern.

[0150] (Step 3) This process involves subjecting the [substrate / organometallic compound layer] laminate, after light irradiation, to a development treatment. During the development treatment, the unexposed parts of the organometallic compound layer are washed away, while the exposed parts remain in close contact with the substrate.

[0151] For the developing process, alkaline aqueous solutions or organic solvents can be used, either individually or in combination of two or more.

[0152] Examples of the aforementioned alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0153] Examples of the organic solvent include those similar to those used in photoresists. In particular, it is preferable to include at least one selected from polyhydric alcohols, esters, ethers, ketones, and aromatic hydrocarbons, especially to include at least an ester, and most preferably to include at least butyl acetate.

[0154] Examples of development methods include applying the developer solution to the [substrate / organometallic compound layer] laminate by methods such as dipping, showering, or spraying.

[0155] The temperature of the developing solution is, for example, 25-40°C. The development time is determined appropriately depending on the thickness of the organometallic compound layer, but is typically around 0.5-5 minutes.

[0156] During the development process, it is ideal that there is a clear contrast between the dissolvable and insoluble parts of the coating in the developer solution, and that the dissolved parts are completely removed. This is because the presence of development residue can easily lead to problems such as abnormal wiring shapes. Furthermore, since the metal resist of the present invention contains organometallic compounds with high dispersibility and thermal stability, the unexposed parts can be easily and completely removed by washing with the developer solution, and no development residue is generated. Therefore, products without defects can be manufactured with a high yield.

[0157] After step 3, a resist film with a fine pattern of high precision can be formed on the substrate. In particular, when using the metal resist, a resist film with a fine pattern of high precision and excellent etching resistance can be formed.

[0158] By using the resist film obtained in this way to etch a substrate, high-precision electronic devices can be manufactured.

[0159] The aforementioned electronic devices include, for example, display devices such as organic EL displays and liquid crystal displays; input devices such as touch panels; light-emitting devices; sensor devices; and MEMS (Micro Electro Mechanical Systems) devices such as optical scanners, optical switches, accelerometers, pressure sensors, gyroscopes, microfluidics, and inkjet heads.

[0160] The configurations and combinations thereof described above are merely examples, and additions, omissions, substitutions, and modifications to the configurations are permitted as appropriate, without departing from the spirit of the present invention. [Examples]

[0161] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples.

[0162] Example 1 (Preparation of nonionic oxime compounds) 2.1 g (0.010 mol) of 3-(2,4-difluorobenzoyl)propionic acid was dissolved in 10 g of acetonitrile, and then 2.0 g (0.030 mol) of 50% hydroxylamine aqueous solution was added dropwise at 30°C, and the mixture was stirred for 6 hours. The precipitate was collected by filtration, the slurry was washed with 100 mL of 1% hydrochloric acid aqueous solution, and then the precipitate was collected again by filtration and vacuum drying to obtain a solid. The obtained solid was dissolved in 100 g of dichloromethane and 2.0 g (0.020 mol) of triethylamine. Then, 1.5 g (0.015 mol) of acetic anhydride was added dropwise under ice cooling, and the mixture was stirred for 1 hour. Next, 100 mL of 1% hydrochloric acid aqueous solution was added and stirred. After that, the aqueous layer was removed to obtain the dichloromethane layer. The obtained dichloromethane layer was washed twice with 100 mL of deionized water. After washing, the dichloromethane layer was concentrated and recrystallized with ethyl acetate / hexane. This yielded 1.7 g of compound (P-1).

[0163] (Preparation of organometallic compounds) 3 g of hafnium isopropoxide was dissolved in 20 g of THF. To this, a solution prepared by dissolving 2 g of benzoic acid, 2 g of acrylic acid, and 1 g of compound (P-1) obtained in Example 1 in 20 g of THF was added at room temperature to obtain a mixed solution. The resulting mixed solution was kept at a controlled temperature of 65°C, and 2 mL of deionized water was added to carry out a sol-gel reaction for 24 hours. After the reaction was complete, the precipitate was collected and washed with acetone / water (1:4, by volume). Then, it was dried under vacuum at 40°C for 24 hours. This yielded an organometallic compound.

[0164] (Preparation of photoresist) 0.1 g of the obtained organometallic compound was dissolved in 3.0 g of PGMEA, and then filtered through a 0.20 μm pore size filter to remove insoluble aggregates. This yielded photoresist (R-1).

[0165] Example 2 (Preparation of nonionic oxime compounds) 2.7 g (0.010 mol) of 2-bromo-4'-(trifluoromethyl)acetophenone and 0.3 g (0.030 mol) of triethylamine were dissolved in 10 g of acetonitrile. Then, under temperature control at 60°C, 1.2 g (0.012 mol) of mercaptoacetic acid was added dropwise, and the mixture was reacted for 6 hours. Subsequently, 2.0 g (0.030 mol) of a 50% hydroxylamine aqueous solution was added dropwise at 30°C, and the mixture was stirred for 6 hours. The precipitate was collected by filtration, the slurry was washed with 100 mL of a 1% hydrochloric acid aqueous solution, and then the precipitate was collected again by filtration and vacuum drying to obtain a solid. The obtained solid was dissolved in 100 g of dichloromethane and 2.0 g (0.020 mol) of triethylamine. Then, 2.0 g (0.015 mol) of benzoyl chloride was added dropwise under ice cooling, and the mixture was stirred for 1 hour. Next, 100 mL of 1% hydrochloric acid aqueous solution was added and stirred. After that, the aqueous layer was removed to obtain the dichloromethane layer. The obtained dichloromethane layer was washed twice with 100 mL of deionized water. After washing, the dichloromethane layer was concentrated and recrystallized with ethyl acetate / hexane. This yielded 2.2 g of compound (P-2).

[0166] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-2) was used instead of compound (P-1), and a photoresist (R-2) was obtained.

[0167] Example 3 (Preparation of nonionic oxime compounds) 1.4 g (0.010 mol) of 2,6-difluoroanisole, 1.7 g (0.010 mol) of tetrafluorosuccinic acid, and 100 g of dichloromethane were dissolved in a solution to which 4.0 g (0.030 mol) of aluminum chloride was added in portions. The mixture was then stirred for 2 hours. Next, 200 g of water was slowly added and stirred for 2 hours, after which the aqueous layer was removed to obtain the dichloromethane layer. The obtained dichloromethane layer was washed twice with water and then concentrated. Next, this concentrate was dissolved in 10 g of acetonitrile, and then 2.0 g (0.030 mol) of 50% aqueous hydroxylamine solution was added dropwise at 30°C and stirred for 6 hours. The precipitate was collected by filtration and the slurry was washed with 100 mL of 1% aqueous hydrochloric acid solution, then filtered again and vacuum dried to obtain the solid. The obtained solid was dissolved in 100 g of dichloromethane and 1.6 g (0.020 mol) of pyridine. Then, 2.7 g (0.010 mol) of pentafluorobenzenesulfonyl chloride was added dropwise under ice cooling, and the mixture was stirred for 1 hour. Next, 100 mL of 1% hydrochloric acid aqueous solution was added and stirred, and then the aqueous layer was removed to obtain the dichloromethane layer. The obtained dichloromethane layer was washed twice with 100 mL of deionized water. After washing, the dichloromethane layer was concentrated and recrystallized with ethyl acetate / hexane to obtain 2.9 g of compound (P-3).

[0168] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-3) was used instead of compound (P-1), and a photoresist (R-3) was obtained.

[0169] Example 4 (Preparation of nonionic oxime compounds) Compound (P-4) 2.2 g was obtained in the same manner as in Example 2, except that 2-bromo-4'-(trifluoromethyl)acetophenone was replaced with 2.2 g (0.010 mol) of 5-acetyl-2-chlorobenzotrifluoride and benzoyl chloride was replaced with heptafluoropropionate chloride.

[0170] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-4) was used instead of compound (P-1), and a photoresist (R-4) was obtained.

[0171] Example 5 (Preparation of nonionic oxime compounds) Compound (P-5) 2.2 g was obtained by following the same procedure as in Example 3, except that 2,6-difluoroanisole was replaced with 2.1 g (0.030 mol) of benzene, tetrafluorosuccinic acid was replaced with 2.2 g (0.010 mol) of tetrafluorophthalic anhydride, and pentafluorobenzenesulfonyl chloride was replaced with butanesulfonyl chloride.

[0172] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-5) was used instead of compound (P-1), and a photoresist (R-5) was obtained.

[0173] Comparative Example 1 (Preparation of nonionic oxime compounds) Compound (P-6) 1.8 g was obtained by the same procedure as in Example 1, except that 3-(2,4-difluorobenzoyl)propionic acid was replaced with acetophenone.

[0174] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-6) was used instead of compound (P-1), and a photoresist (R-6) was obtained.

[0175] Comparative Example 2 (Preparation of nonionic oxime compounds) Compound (P-7) 2.0 g was obtained by following the same procedure as in Example 1, except that 3-(2,4-difluorobenzoyl)propionic acid was replaced with 4-(trifluoroacetyl)anisole and acetic anhydride was replaced with butanesulfonic acid chloride.

[0176] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-7) was used instead of compound (P-1), and a photoresist (R-7) was obtained.

[0177] Comparative Example 3 (Preparation of nonionic oxime compounds) Compound (P-8) 2.3 g was obtained by following the same procedure as in Example 1, except that 3-(2,4-difluorobenzoyl)propionic acid was replaced with 3-benzoylpropionic acid.

[0178] (Preparation of organometallic compounds and photoresists) An organometallic compound was obtained in the same manner as in Example 1, except that the obtained compound (P-8) was used instead of compound (P-1), and a photoresist (R-8) was obtained.

[0179] The solvent solubility of compounds (P-1) to (P-8) obtained in the examples and comparative examples, and the photosensitivity of photoresists (R-1) to (R-8) obtained in the examples and comparative examples were evaluated by the following method.

[0180] (Solvent solubility evaluation) 0.2 g of each compound (P-1) to (P-8) was placed in a test tube, and 0.2 to 0.5 g of PGMEA was added at a temperature of 25°C until the compound was completely dissolved. The compound concentration (wt%) at the point of complete dissolution was used as an indicator of solvent solubility. If the compound did not completely dissolve even after adding 30 g of PGMEA, it was evaluated as not dissolving. The results are shown in the table below.

[0181] (Photosensitivity evaluation) On a substrate treated with hexamethyldisilazane, photoresists (R-1) to (R-8) were applied using a spin coater, and then the solvent was removed by heating at 80°C for 60 seconds to obtain a coating with a thickness of approximately 50 nm. The obtained coating film was placed in BL-3 of the NewSUBARU Synchrotron Radiation Facility at the University of Hyogo, and irradiated with 13.5 nm synchrotron radiation, with irradiation times varied from 1 to 30 seconds. After that, the coating film was developed by immersing it in butyl acetate for 30 seconds and then dried. After development and drying, the exposed areas of the paint film were observed under a microscope, and the minimum exposure dose (Eth) required to achieve a paint film thickness of 40 nm or more in the irradiated area was measured. The ratio of the minimum exposure dose (Eth) to the minimum exposure dose (Eth') when using the photoresist (R-6) obtained in Comparative Example 1 was calculated using the following formula and used as an indicator of photosensitivity. A smaller minimum exposure dose ratio indicates better photosensitivity. Minimum exposure ratio = Eth / Eth'

[0182] [Table 1]

[0183] [Table 2]

[0184] In summary, the configuration of the present invention and its variations are described below. [1] Equation (1-1) or (1-2) (wherein Ar 1 Ar 2 These are identical or different structures, representing an aromatic ring structure, or a structure in which two or more aromatic rings are linked by a single bond or a linking group. 1 R represents an -O(C=O)R group, an -OS(=O)2R group, or an -OPO(OR)2 group, where R represents a hydrocarbon group or a halogenated hydrocarbon group. 2 , R 5 Each of these independently represents a single bond or a linking group. 3 R represents a halogen atom or a halogenated hydrocarbon group.4 The compound is represented as follows: a hydrocarbon group which may have substituents, a group in which two or more hydrocarbon groups which may have substituents are bonded together by a single bond or a linking group, or a cyano group. (n1 is an integer from 1 to 5, and n2 is an integer from 1 to 4). [2] The above R 3 The compound according to [1], wherein is a fluorine atom or a trifluoromethyl group. [3] Organometallic compounds having a configuration in which a metal or metal oxide (1) is coordinated with the compound described in [1] or [2]. [4] The organometallic compound according to [3], wherein (1) is at least one selected from hafnium, zirconium, tin, cobalt, palladium, antimony, and oxides thereof. [5] A photosensitive material for resists containing the organometallic compound described in [3] or [4]. [6] The photosensitive material for resists described in [5], which is a photosensitive material for extreme ultraviolet light or an electron beam.

Claims

1. A compound represented by the following formula (1-1-1) or (1-2-1). 【Chemistry 1】 (In the formula, R 1 is -O(C=O)R group, -OS(=O) ２ R group, or -OPO(OR) ２ The group is represented by R, where R represents an alkyl group, an aryl group, an alkyl halogenated group, or an aryl halogenated group. R2 represents an alkylene group, a halogenated alkylene group, or a divalent group formed by two or more of these groups being linked via ether bonds or thioether bonds. R ３ This indicates a halogen atom or a halogenated hydrocarbon group. R ４ This represents a C1-5 alkyl group or a C6-10 aryl group. R 5 represents an alkylene group, a halogenated alkylene group, a divalent group formed by these groups being bonded to an ether bond or a thioether bond, or a single bond. n1 represents an integer between 1 and 5, and n2 represents an integer between 1 and 4.

2. The aforementioned R ３ The compound according to claim 1, wherein is a fluorine atom or a trifluoromethyl group.

3. An organometallic compound having a configuration in which the compound described in claim 1 or 2 is coordinately bonded to a metal or metal oxide (1).

4. The organometallic compound according to claim 3, wherein (1) is at least one selected from hafnium, zirconium, tin, cobalt, palladium, antimony, and oxides thereof.

5. A photosensitive material for resists comprising the organometallic compound described in claim 3.

6. The photosensitive material for resists according to claim 5, which is a photosensitive material for extreme ultraviolet light or an electron beam.

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