Resist composition, method for producing resist composition, substrate processing apparatus, and substrate processing method

Abstract

The resist composition contains at least one compound represented by general formulae (1), (2), and (3).

Description

Technical Field

[0001] This disclosure relates to a resist composition, a method for manufacturing the resist composition, a substrate processing apparatus, and a substrate processing method. Background Technology

[0002] The photosensitive agent chemically amplified resist (PSCAR) used for EUV exposure comprises: a photoacid generator that produces acid upon absorbing EUV light, and a photosensitive agent that changes its light absorption mode upon activation by acid. In the PSCAR process, the photoacid generator is exposed to EUV light, the photosensitive agent activated by the generated acid absorbs EUV light, and further produces acid from the photoacid generator through energy transfer and other processes.

[0003] Patent document 1 discloses a technique for using a compound that changes from an acetal structure to a ketone structure through external stimulation (light, acid, etc.) as a photosensitizer precursor used in the PSCAR process for EUV exposure.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-188458 Summary of the Invention

[0007] The problem the invention aims to solve

[0008] In existing technologies, when the photosensitizer precursor changes from an acetal structure to a ketone structure, the conjugated ranges are connected and the absorption wavelength is lengthened, but there is no change in polarity. Therefore, the solubility during development is not significantly different, and the solubility contrast cannot be fully obtained.

[0009] The subject of this disclosure is to provide a resist composition capable of improving dissolution contrast.

[0010] Solution for solving the problem

[0011] One type of resist composition disclosed herein contains at least one compound represented by the following general formulas (1), (2) and (3).

[0012]

[0013] In general formula (1), R1 to R4 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted).

[0014] X1 and Y1 are each independently selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

[0015]

[0016] In general formula (2), R5 to R9 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms that has substituted groups; an alkenyl group with 1 to 12 carbon atoms that has substituted groups; an aryl group with 6 to 14 carbon atoms that has substituted groups; and a heteroaryl group with 4 to 12 carbon atoms that has substituted groups.

[0017] X2 can be any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom.

[0018] Y2 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0019]

[0020] In general formula (3), R 10 ~R 15 Each of the following is independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0021] X3 can be any one of the following groups: carbon atoms, silicon atoms, germanium atoms, and tin atoms.

[0022] Y3 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0023] The effects of the invention

[0024] According to one aspect of this disclosure, a resist composition capable of improving dissolution contrast can be obtained. Attached Figure Description

[0025] Figure 1 This is a graph showing the absorption wavelength of the photosensitizer (photosensitizer precursor) used in the resist composition before activation.

[0026] Figure 2 It means Figure 1 The diagram shows the absorption wavelengths of the photosensitizer after activation.

[0027] Figure 3 This is a diagram showing the composition of the resist composition.

[0028] Figure 4 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and the acid-generating agent (PAG) bond).

[0029] Figure 5 It means Figure 4 The diagram shows the reaction of the resist composition to be activated.

[0030] Figure 6 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer bonded to the photoresist substrate).

[0031] Figure 7 It means Figure 6 A figure showing an example of an anti-corrosion composition.

[0032] Figure 8 It means Figure 6 A figure showing an example of an anti-corrosion composition.

[0033] Figure 9 It means Figure 6 A figure showing an example of an anti-corrosion composition.

[0034] Figure 10 It means Figure 7 The diagram shows the reaction of the resist composition to be activated.

[0035] Figure 11 It means Figure 8 The diagram shows the reaction of the resist composition to be activated.

[0036] Figure 12 It means Figure 8 A figure showing a specific example of an anti-corrosion composition.

[0037] Figure 13 This is a diagram showing the composition of the photoresist composition (the composition of the bonding between the acid-generating agent (PAG) and the photoresist substrate, and the bonding between the photosensitizer and the acid-generating agent (PAG)).

[0038] Figure 14 This is a diagram showing the composition of the resist composition (the composition of the photosensitizer and quencher (PDB) bond).

[0039] Figure 15 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and the photoresist substrate ion bond).

[0040] Figure 16 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and the photoresist substrate ion bond).

[0041] Figure 17A This is a diagram illustrating the existing process for chemically amplifying photoresist using photosensitizers.

[0042] Figure 17B This is a diagram illustrating the existing process for chemically amplifying photoresist using photosensitizers.

[0043] Figure 17C This is a diagram illustrating the existing process for chemically amplifying photoresist using photosensitizers.

[0044] Figure 18A This is a diagram illustrating the process of using a photosensitizer chemically amplified resist with the resist composition disclosed herein.

[0045] Figure 18B This is a diagram illustrating the process of using a photosensitizer chemically amplified resist with the resist composition disclosed herein.

[0046] Figure 18C This is a diagram illustrating the process of using a photosensitizer chemically amplified resist with the resist composition disclosed herein.

[0047] Figure 19 This is a diagram illustrating a method of manufacturing the resist composition disclosed herein.

[0048] Figure 20 This is a diagram illustrating a method of manufacturing the resist composition disclosed herein.

[0049] Figure 21 This is a diagram illustrating a method of manufacturing the resist composition disclosed herein.

[0050] Figure 22 This is a diagram illustrating a substrate processing apparatus using the resist composition disclosed herein.

[0051] Figure 23 This is a diagram illustrating a substrate processing apparatus using the resist composition disclosed herein.

[0052] Figure 24 This is a diagram illustrating a substrate processing apparatus using the resist composition disclosed herein.

[0053] Figure 25 This is a diagram illustrating a substrate processing apparatus using the resist composition disclosed herein. Detailed Implementation

[0054] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. It should be noted that common parts in the various figures are sometimes labeled with the same or corresponding reference numerals and their descriptions are omitted.

[0055] <Corrosion Resistance Composition>

[0056] The resist compositions disclosed herein contain at least one compound represented by the following general formulas (4), (5), and (6). These compounds can function as photosensitizers (precursors to photosensitizers) in the resist compositions.

[0057]

[0058]

[0059]

[0060] The compound represented by general formula (1) has a heterocycle with three six-membered rings fused together in the compound, namely C 13 H 10 The framework of X1 (where X1 is a group 16 element of the periodic table other than Po) (hereinafter, sometimes referred to as the Xanthylium framework or Xanthylium structure).

[0061] In general formula (1), R1 to R4 are each independently selected from any one of the following groups: alkyl groups with 1 to 12 carbon atoms that are straight-chain, branched, or cyclic with substituents; alkenyl groups with 1 to 12 carbon atoms that are straight-chain, branched, or cyclic with substituents; aryl groups with 6 to 14 carbon atoms that are substituted; and heteroaryl groups with 4 to 12 carbon atoms that are substituted. X1 and Y1 are each independently selected from any one of the following groups: oxygen (O) atom, sulfur (S) atom, selenium (Se) atom, and tellurium (Te) atom.

[0062] In the compounds represented by general formula (1), the alkyl group having 1 to 12 carbon atoms, which is a straight chain, branched chain, or cyclic group, can be exemplified by, for example, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and norbornane-2-yl, etc.

[0063] As an alkenyl group having 1 to 12 carbon atoms in a straight chain, branched chain, or cyclic shape with optional substituents, examples include groups formed by replacing at least one carbon-carbon single bond of the aforementioned alkyl group with a carbon-carbon double bond.

[0064] Aryl groups with 6 to 14 carbon atoms that are optionally substituents can be exemplified by monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups obtained by fusion of at least two rings of the monocyclic aromatic hydrocarbon.

[0065] As a heteroaryl group having 4 to 12 carbon atoms as an optional substituent, examples include groups comprising at least one carbon atom selected from oxygen, nitrogen, and sulfur atoms in place of the aforementioned aryl group.

[0066] In the compounds represented by general formula (1), it is preferable that X1 is an oxygen atom or a sulfur atom, and more preferably that X1 is an oxygen atom.

[0067] The compound shown in general formula (2) has a heterocycle with three six-membered rings fused together in the compound, namely C 13 H 10 The framework of X2 (where X2 is a group 15 element in the periodic table other than Bi) (hereinafter sometimes referred to as the acridine framework or acridine structure).

[0068] In general formula (2), R5 to R9 are each independently selected from any of the following groups: alkyl groups with 1 to 12 carbon atoms that are straight-chain, branched, or cyclic with substituents; alkenyl groups with 1 to 12 carbon atoms that are straight-chain, branched, or cyclic with substituents; aryl groups with 6 to 14 carbon atoms that are substituents; and heteroaryl groups with 4 to 12 carbon atoms that are substituents; X2 is selected from any of the following groups: nitrogen (N) atom, phosphorus (P) atom, arsenic (As) atom, and antimony (Sb) atom; and Y2 is selected from any of the following groups: oxygen atom, sulfur atom, selenium atom, and tellurium atom.

[0069] In the compounds shown in general formula (2), the alkyl groups having 1 to 12 carbon atoms, which are straight-chain, branched, or cyclic, and which may optionally have substituents, can be listed as alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and norbornane-2-yl.

[0070] As an alkenyl group having 1 to 12 carbon atoms in a straight chain, branched chain, or cyclic shape with optional substituents, examples include groups formed by replacing at least one carbon-carbon single bond of the aforementioned alkyl group with a carbon-carbon double bond.

[0071] Aryl groups with 6 to 14 carbon atoms that are optionally substituents can be exemplified by monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups obtained by fusion of at least two rings of the monocyclic aromatic hydrocarbon.

[0072] As a heteroaryl group having 4 to 12 carbon atoms as an optional substituent, examples include groups comprising at least one carbon atom selected from oxygen, nitrogen, and sulfur atoms in place of the aforementioned aryl group.

[0073] In the compounds represented by general formula (2), it is preferable that X2 is a nitrogen atom or a phosphorus atom, and more preferably that X2 is a nitrogen atom.

[0074] The compound represented by general formula (3) has a heterocycle with three six-membered rings fused together in the compound, namely C 13 H 10The framework of X3 (where X3 is a group 14 element of the periodic table other than Pb) (hereinafter, sometimes referred to as the anthracene framework or anthracene structure).

[0075] In addition, in general formula (3), R 10 ~R 15 Each of the following is independently selected from any one of the following groups: alkyl groups having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); alkenyl groups having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); aryl groups having 6 to 14 carbon atoms (either substituted); and heteroaryl groups having 4 to 12 carbon atoms (either substituted); X3 is selected from any one of the following groups: carbon (C) atom, silicon (Si) atom, germanium (Ge) atom, and tin (Sn) atom; and Y3 is selected from any one of the following groups: oxygen atom, sulfur atom, selenium atom, and tellurium atom.

[0076] In the compounds shown in general formula (3), the alkyl groups having 1 to 12 carbon atoms, which are straight-chain, branched, or cyclic, and which may optionally have substituents, can be listed as alkyl groups such as methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantane-1-yl, adamantane-2-yl, norbornane-1-yl, and norbornane-2-yl.

[0077] As an alkenyl group having 1 to 12 carbon atoms in a straight chain, branched chain, or cyclic shape with optional substituents, examples include groups formed by replacing at least one carbon-carbon single bond of the aforementioned alkyl group with a carbon-carbon double bond.

[0078] Aryl groups with 6 to 14 carbon atoms that are optionally substituents can be exemplified by monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups obtained by fusion of at least two rings of the monocyclic aromatic hydrocarbon.

[0079] As a heteroaryl group having 4 to 12 carbon atoms as an optional substituent, examples include groups comprising at least one carbon atom selected from oxygen, nitrogen, and sulfur atoms to replace the aforementioned aryl group.

[0080] In the compounds represented by general formula (3), it is preferable that X3 is a carbon atom or a silicon atom, and more preferably that X3 is a silicon atom.

[0081] The resist composition disclosed herein may contain a compound represented by the following general formula (7). The compound represented by general formula (7) is a compound that is activated by absorbing ultraviolet light from the compound represented by the above general formula (1).

[0082]

[0083] In general formula (7), R1 to R3 are each independently selected from any one of the following groups: an alkyl group with 1 to 12 carbon atoms that is either straight-chain, branched or cyclic with substituents; an alkenyl group with 1 to 12 carbon atoms that is either straight-chain, branched or cyclic with substituents; an aryl group with 6 to 14 carbon atoms that is either substituents; and a heteroaryl group with 4 to 12 carbon atoms that is either substituents. X1 is an oxygen atom or a sulfur atom.

[0084] The compound shown in general formula (7) has the same tandem skeleton as the compound shown in general formula (1) above, but is different in that it is a polar cation obtained by removing R4-Y1- from the 10 position of the tandem skeleton.

[0085] The resist composition disclosed herein may contain a compound of general formula (8) that has been activated from the compound of general formula (2) above.

[0086]

[0087] In general formula (8), R5 to R8 are each independently selected from any one of the following groups: a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms that has a substituent; an alkenyl group with 1 to 12 carbon atoms that has a substituent; an aryl group with 6 to 14 carbon atoms that has a substituent; and a heteroaryl group with 4 to 12 carbon atoms that has a substituent; and X2 is selected from any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom.

[0088] The compound shown in general formula (8) has the same acridine-onium skeleton as the compound shown in general formula (2), but differs in that it is a polar cation obtained by removing R6 from the 5 position (X2) of the acridine-onium skeleton and removing R9-Y2- from the 10 position of the acridine-onium skeleton.

[0089] The compound represented by general formula (8) is preferably a compound in which X2 is a nitrogen atom, i.e., a compound represented by general formula (9) below.

[0090]

[0091] In general formula (9), R5 to R8 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms that is either straight-chain, branched, or cyclic with substituents; an alkenyl group having 1 to 12 carbon atoms that is either straight-chain, branched, or cyclic with substituents; an aryl group having 6 to 14 carbon atoms that is either substituents; and a heteroaryl group having 4 to 12 carbon atoms that is either substituents.

[0092] The resist composition disclosed herein may contain a compound represented by general formula (3). The compound represented by general formula (3) is a compound represented by general formula (10) that is activated by absorbing ultraviolet light.

[0093]

[0094] In general formula (10), R 10 ~R 14 Each of the following is independently selected from the group consisting of a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with a substituent; an alkenyl group having 1 to 12 carbon atoms with a substituent; an aryl group having 6 to 14 carbon atoms with a substituent; and a heteroaryl group having 4 to 12 carbon atoms with a substituent, wherein X3 is selected from the group consisting of carbon atoms, silicon atoms, germanium atoms, and tin atoms.

[0095] The compounds represented by general formula (10) and those represented by general formula (3) share the presence of an anthracene skeleton, but differ in that they possess R. 11 Separation from position 5 (X3) of the anthracene skeleton, R 15 -Y3- is the structure obtained by removing the 10 position from the anthracene skeleton. It should be noted that the compound shown in general formula (10) is a weakly cationic compound with a slight electron shift (polarity) at the 5 position of the anthracene skeleton.

[0096] Figure 1 This is a graph showing the absorption wavelength of the photosensitizer precursor (the compound shown in the above general formulas (1) and (2)) used in the resist composition of this disclosure before absorbing ultraviolet light (before activation). Figure 2 It means Figure 1 A graph showing the absorption wavelengths of the photosensitizer precursor (the compound shown in the above general formulas (1) and (2)) after absorbing ultraviolet light (after activation) and the photosensitizer (the compound shown in the above general formulas (7) and (8)).

[0097] Figure 1 In the medium, the photosensitizer precursor before absorbing ultraviolet light (before activation) exhibits an absorption peak around 250nm~300nm. In contrast, Figure 2 In the process, the photosensitizer precursor absorbs ultraviolet light (after activation), and the photosensitizer shows an absorption wavelength peak in the vicinity of 350nm~400nm.

[0098] That is, it is expected that the compounds shown in the above general formulas (4) to (6) (compounds having tonne, acridine, and anthracene structures) will change into the compounds shown in the above general formulas (7) to (10) respectively by absorbing ultraviolet light, thus increasing the absorption wavelength. Therefore, by using the compounds shown in the above general formulas (4) to (6) as photosensitizer precursors, when irradiating with UV light once in the process after EUV exposure, the photosensitizer that changes into the compounds shown in the above general formulas (7) to (10) can be treated with ultraviolet light close to visible light.

[0099] Furthermore, the compounds represented by general formulas (4) to (6) are nonpolar before absorbing ultraviolet light, but become polar compounds represented by general formulas (7) to (10) after absorbing ultraviolet light. Therefore, when UV is irradiated once in the process after EUV exposure, the removal of the compounds represented by general formulas (7) to (10) becomes easier, and an improvement in dissolution contrast can be expected.

[0100] Figure 3 This is a diagram showing the composition of the resist composition. The resist composition disclosed herein is a composition comprising a resist substrate 1 and a photosensitizer 2, and may contain an acid-generating agent 3.

[0101] The resist substrate 1 represents a polymer component that is soluble or insoluble in the developer solution due to the action of an acid. The polymer represents a compound obtained by polymerizing two or more monomers, including copolymers obtained by polymerizing two or more monomers. Furthermore, the action of the acid indicates at least one of the following: the acid functions as a reactant or as a catalyst.

[0102] There are no particular limitations on the polymer components, and examples include: a first polymer (hereinafter also called "[A] polymer") having a structural unit (hereinafter also called "structural unit (I)") containing a group that generates a polar group through the action of an acid (hereinafter also called "acid-dissociating group"). In addition, as a polymer component other than the polymer components, a second polymer (hereinafter also called "[B] polymer") that does not contain structural unit (I) may be further included.

[0103] [A] Polymer or [B] polymer may further have: a structural unit containing a fluorine atom (hereinafter also referred to as "structural unit (II)"), a structural unit containing a phenolic hydroxyl group (III) and a structural unit (IV) containing a lactone structure, a cyclic carbonate structure, a sulfonyl lactone structure or a combination thereof, and may further have other structural units other than structural units (I) to structural units (IV).

[0104] [A] The polymer may further have structural units (II) to (IV) and / or other structural units. [B] The polymer is different from the polymer in [A]. [B] The polymer preferably has structural unit (II), but may also have structural units (III) and (IV), or other structural units besides structural units (III) to (IV).

[0105] The lower limit for the proportion of structural unit (I) relative to all structural units constituting polymer [A] is preferably 10 mol%, more preferably 20 mol%, further preferably 25 mol%, and particularly preferably 30 mol%. On the other hand, the upper limit for the above-mentioned proportion is preferably 80 mol%, more preferably 70 mol%, further preferably 65 mol%, and particularly preferably 60 mol%. By setting the above-mentioned proportion within the above range, the dissolution contrast of the patterned exposed and unexposed areas of the resist composition film formed from this resist composition with respect to the developer can be sufficiently ensured, resulting in improved resolution and the like.

[0106] When polymer [A] has structural unit (II), the lower limit of the content ratio of structural unit (II) relative to all structural units constituting polymer [A] is preferably 3 mol%, more preferably 5 mol%, and even more preferably 10 mol%. On the other hand, the upper limit of the above-mentioned content ratio is preferably 40 mol%, more preferably 35 mol%, and even more preferably 30 mol%. By setting the above-mentioned content ratio within the above range, the sensitivity when using EUV or the like for pattern exposure is further improved. On the other hand, if the above-mentioned content ratio is greater than the above-mentioned upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be reduced.

[0107] When the polymer composition includes polymer [B] and polymer [B] has structural unit (II), the lower limit of structural unit (II) relative to all structural units constituting polymer [B] is preferably 3 mol%, more preferably 5 mol%, and even more preferably 10 mol%. On the other hand, the upper limit of the above-mentioned content ratio is preferably 40 mol%, more preferably 35 mol%, and even more preferably 30 mol%. By setting the above-mentioned content ratio within the above range, the sensitivity when using EUV or the like as pattern exposure light can be further improved. On the other hand, if the above-mentioned content ratio is greater than the above-mentioned upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be reduced.

[0108] By incorporating structural unit (III) into polymer [A] or polymer [B], the sensitivity when irradiated with KrF excimer laser, EUV (extreme ultraviolet), electron beam, etc., during the patterning exposure process described later can be further improved.

[0109] When the [A] polymer has structural unit (III), the lower limit of the content of structural unit (III) relative to all structural units constituting the [A] polymer is preferably 1 mol%, more preferably 30 mol%, and even more preferably 50 mol%. On the other hand, the upper limit of the above-mentioned content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 75 mol%. By setting the content of structural unit (III) within the above range, the sensitivity of the resist composition can be further improved.

[0110] When the polymer component includes polymer [B] and polymer [B] has structural unit (III), the lower limit of the content ratio of structural unit (III) relative to all structural units constituting polymer [B] is preferably 1 mol%, more preferably 30 mol%, and even more preferably 50 mol%. On the other hand, the upper limit of the above-mentioned content ratio is preferably 90 mol%, more preferably 80 mol%, and even more preferably 75 mol%. By setting the content ratio of structural unit (III) within the above range, the sensitivity of the resist composition can be further improved.

[0111] It should be noted that structural unit (III) can be formed by the following method: after polymerizing a monomer in which the hydrogen atom of the -OH group of an aromatic ring containing a phenolic hydroxyl group is replaced by an acetyl group or the like, the resulting polymer is subjected to a hydrolysis reaction in the presence of an amine.

[0112] Polymers [A] and [B], by further incorporating structural units (IV), can have their solubility in the developer adjusted to be more moderate, resulting in further improvement in the photolithography performance of the resist composition. This enhances the adhesion between the resist film formed from the resist composition and the substrate. Here, a lactone structure refers to a structure having a single ring (lactone ring) containing a group represented by -OC(O)-. A cyclic carbonate structure refers to a structure having a single ring (cyclic carbonate ring) containing a group represented by -OC(O)-O-. A sulfonyl lactone structure refers to a structure having a single ring (sulfonyl lactone ring) containing a group represented by -OS(O)2-.

[0113] As structural unit (IV), preferably, structural units comprising a norbornene lactone structure, structural units comprising an oxa-norbornene lactone structure, structural units comprising a γ-butyrolactone structure, structural units comprising an ethylene carbonate structure, and structural units comprising a norbornene sulfonyl lactone structure are preferred. More preferably, structural units derived from norbornene lactone-yl (meth)acrylate, structural units derived from oxa-norbornene lactone-yl (meth)acrylate, structural units derived from cyano-substituted norbornene lactone-yl (meth)acrylate, structural units derived from norbornene lactone-yl (meth)acrylate oxycarbonyl methyl ester, and structural units derived from butyrolactone-3-yl (meth)acrylate are preferred. Units, structural units derived from butyrolactone-4-yl(meth)acrylate, structural units derived from 3,5-dimethylbutyrolactone-3-yl(meth)acrylate, structural units derived from 4,5-dimethylbutyrolactone-4-yl(meth)acrylate, structural units derived from 1-(butyrolactone-3-yl)cyclohexane-1-yl(meth)acrylate, structural units derived from ethylene carbonate-methyl(meth)acrylate, structural units derived from cyclohexene carbonate-methyl(meth)acrylate, structural units derived from norbornenesulfonyl-methyl(meth)acrylate, and structural units derived from norbornenesulfonyl-methyl(meth)acrylate-oxycarbonyl methyl ester.

[0114] When polymer [A] has structural units (IV), the lower limit of the content ratio of structural units (IV) relative to all structural units constituting polymer [A] is preferably 1 mol%, more preferably 10 mol%, further preferably 20 mol%, and particularly preferably 25 mol%. On the other hand, the upper limit of the above-mentioned content ratio is preferably 70 mol%, more preferably 65 mol%, further preferably 60 mol%, and particularly preferably 55 mol%. By setting the above-mentioned content ratio within the above range, the adhesion between the resist film formed by the resist composition and the substrate can be further improved.

[0115] When the polymer component includes polymer [B] and polymer [B] has structural units (IV), the lower limit of the content ratio of structural units (IV) relative to all structural units constituting polymer [B] is preferably 1 mol%, more preferably 10 mol%, further preferably 20 mol%, and particularly preferably 25 mol%. On the other hand, the upper limit of the above-mentioned content ratio is preferably 70 mol%, more preferably 65 mol%, further preferably 60 mol%, and particularly preferably 55 mol%. By setting the above-mentioned content ratio within the above range, the adhesion between the resist film formed by the resist composition and the substrate can be further improved.

[0116] [Other structural units]

[0117] Polymers [A] and [B] may have other structural units besides the structural units (I) to (IV) described above. Examples of other structural units include, for example, structural units containing polar groups or structural units containing non-dissociable hydrocarbon groups. Examples of polar groups include, for example, alcoholic hydroxyl groups, carboxyl groups, cyano groups, nitro groups, and sulfonamide groups. Examples of non-dissociable hydrocarbon groups include, for example, linear alkyl groups. The upper limit of the content of the aforementioned other structural units relative to all structural units constituting polymer [A] is preferably 20 mol%, more preferably 10 mol%.

[0118] As a minimum total content of polymers [A] and [B], the total solids content of the resist composition is preferably 70% by mass, more preferably 75% by mass, and even more preferably 80% by mass. Here, "total solids content" refers to the components of the resist composition other than the solvent.

[0119] The weight-average molecular weight (Mw) of polymer [A], calculated from polystyrene using gel permeation chromatography (GPC), is not particularly limited. As a lower limit, it is preferably 1000, more preferably 2000, further preferably 3000, and particularly preferably 5000. On the other hand, as an upper limit of the Mw of polymer [A], it is preferably 50000, more preferably 30000, further preferably 20000, and particularly preferably 15000.

[0120] By setting the Mw of polymer [A] within the aforementioned range, the coatability and development defect suppression of the resist composition are improved. If the Mw of polymer [A] is less than the lower limit, it may be impossible to obtain a resist film with sufficient heat resistance. Conversely, if the Mw of polymer [A] is greater than the upper limit, the developability of the resist film may decrease.

[0121] [A] The lower limit of the ratio (Mw / Mn) of the polymer's GPC-based polystyrene equivalent Mw to its number-average molecular weight (Mn) is typically 1. On the other hand, the upper limit of the above ratio is typically 5, preferably 3, and more preferably 2.

[0122] The weight-average molecular weight (Mw) of the polymer [B], calculated from polystyrene using gel permeation chromatography (GPC), is not particularly limited, but a lower limit is preferably 1000, more preferably 2000, further preferably 2500, and particularly preferably 3000. On the other hand, an upper limit for the Mw of the polymer [B] is preferably 50000, more preferably 30000, further preferably 20000, and particularly preferably 15000. By setting the Mw of the polymer [B] within the above range, the coatability and development defect suppression of the resist composition are improved. If the Mw of the polymer [B] is less than the lower limit, it may be impossible to obtain a resist film with sufficient heat resistance. Conversely, if the Mw of the polymer [B] is greater than the upper limit, the developability of the resist film may decrease.

[0123] [B] The lower limit of the ratio (Mw / Mn) of the polymer based on GPC-converted polystyrene is preferably 1. On the other hand, the upper limit of the above ratio is preferably 5, more preferably 3, and even more preferably 2.

[0124] It should be noted that the Mw and Mn values ​​of the polymers in this specification are values ​​determined using gel permeation chromatography (GPC).

[0125] Polymer [A] and polymer [B] may contain low molecular weight components with a molecular weight of 1000 or less. The upper limit for the content of the low molecular weight component in polymer [A] is preferably 1.0% by mass, more preferably 0.5% by mass, and even more preferably 0.3% by mass. The lower limit for the above content is, for example, 0.01% by mass. By setting the content of the low molecular weight components in polymer [A] and polymer [B] within the above range, the photolithographic properties of the resist composition can be further improved.

[0126] It should be noted that the content of low molecular weight components of the polymer in this specification is a value determined using high performance liquid chromatography (HPLC).

[0127] The lower limit for the fluorine atom content in polymers [A] and [B] is preferably 1% by mass, more preferably 2% by mass, further preferably 4% by mass, and particularly preferably 7% by mass. On the other hand, the upper limit for the above-mentioned content is preferably 60% by mass, more preferably 40% by mass, and even more preferably 30% by mass. Here, the fluorine atom content (mass%) of the polymer can be calculated from the structure of the polymer determined by 13C-NMR spectroscopy.

[0128] (Synthetic methods of [A] polymer and [B] polymer)

[0129] [A] Polymer and [B] polymer can be manufactured, for example, by polymerizing monomers corresponding to specified structural units in a suitable polymerization solvent using polymerization initiators such as free radical polymerization initiators. Specific synthesis methods include, for example: adding a solution containing monomers and a free radical polymerization initiator dropwise to a polymerization solvent or a solution containing monomers to carry out the polymerization reaction; adding a solution containing monomers and a solution containing a free radical polymerization initiator dropwise to a polymerization solvent or a solution containing monomers respectively to carry out the polymerization reaction; adding multiple solutions containing various monomers and a solution containing a free radical polymerization initiator dropwise to a polymerization solvent or a solution containing monomers respectively to carry out the polymerization reaction, etc.

[0130] Examples of azo-based free radical initiators for the aforementioned free radical polymerization include azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl 2,2'-azobisisobutyrate; and peroxide-based free radical initiators such as benzoyl peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide. Among these free radical polymerization initiators, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, with AIBN being more preferred. These free radical initiators can be used individually or in combination of two or more.

[0131] As the solvent used in the above polymerization, for example, the same substance that may be contained in the resist composition described later can be used.

[0132] The lower limit of the reaction temperature in the above polymerization is preferably 40°C, more preferably 50°C. On the other hand, the upper limit of the reaction temperature is preferably 150°C, more preferably 120°C. The lower limit of the reaction time in the above polymerization is preferably 1 hour. On the other hand, the upper limit of the reaction time is preferably 48 hours, more preferably 24 hours.

[0133] Polymers [A] and [B] are preferably recovered via reprecipitation. That is, after the reaction is complete, the reaction solution is added to a reprecipitation solvent, thereby recovering the target polymer in powder form. As the reprecipitation solvent, one or more alcohols, alkanes, etc., can be used alone or in combination. Besides reprecipitation, polymers can also be recovered by removing low-molecular-weight components such as monomers and oligomers through liquid-liquid extraction, column chromatography, or ultrafiltration.

[0134] Photosensitizer 2 is a substance that, in a photochemical reaction, is first excited by light by a substance other than the matrix, and then transfers its excitation energy to the matrix through energy transfer and electron transfer, thereby causing a reaction in the matrix.

[0135] In the resist composition disclosed herein, compounds represented by the above general formulas (4) to (10) are used as photosensitizer 2. These photosensitizers may be used alone or in combination of two or more.

[0136] Relative to 100% by mass of the resist composition components other than the acid-generating agent, the content of the photosensitizer in the resist composition of this embodiment is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 15% by mass. If the content of the photosensitizer in the resist composition is within such a range, the activation of the photoacid-generating agent based on the photosensitizer can be improved.

[0137] Acid generator 3, also known as photoacid generator (PAG), produces acid through exposure. Here, "producing acid through exposure" means generating acid by irradiating the acid generator with light, electron beams, or other radiation (active energy lines). The acid generated by the acid generator acts on the polymer component in a manner that makes the polymer component soluble or insoluble in the developing solution.

[0138] For example, when an acid-producing agent is irradiated with a first radiation having a wavelength below 300 nm but not with a second radiation having a wavelength greater than 300 nm, the light absorption wavelength can be changed to absorb the second radiation.

[0139] Here, the first radiation is an energy ray with a wavelength of 300 nm or less (e.g., extreme ultraviolet (EUV) radiation). There is no limitation on the wavelength range of the first radiation as long as it is 300 nm or less, preferably 250 nm or less, and more preferably 200 nm or less.

[0140] On the other hand, the second radiation is an energy ray with a wavelength greater than 300 nm or less (e.g., ultraviolet (UV) radiation other than extreme ultraviolet radiation). There is no limitation on the wavelength range of the second radiation as long as it is greater than 300 nm, preferably 500 nm or less, and more preferably 400 nm or less.

[0141] In this specification, the case of irradiation with the first radiation but not with the second radiation indicates the state of irradiation with only the first radiation and not with the second radiation. Furthermore, the change in light absorption wavelength is represented by absorption of the second radiation, indicating a shift or displacement of the maximum absorption wavelength of the radiation from the wavelength region of the first radiation to the wavelength region of the second radiation.

[0142] Furthermore, the acid-producing agent decomposes when irradiated with the second radiation after irradiation with the first radiation, but does not decompose when irradiated with the second radiation without irradiation with the first radiation. Here, "irradiation with the second radiation without irradiation with the first radiation" refers to the state where only the second radiation is irradiated and not the first radiation. Similarly, "irradiation with the second radiation after irradiation with the first radiation" refers to the state where only the first radiation is irradiated and then only the second radiation is irradiated. Moreover, "decomposition of the acid-producing agent" means that the acid-producing agent transforms into two or more other components while simultaneously producing acid.

[0143] In the resist composition of this embodiment, the acid-generating agent can increase its polarity through the action of acid. Increased polarity means a larger charge deviation and increased hydrophilicity. By increasing its polarity, the acid-generating agent has higher solubility in hydrophilic developers such as organic alkali solutions, and lower solubility in hydrophobic developers such as organic solvents.

[0144] In the resist composition of this embodiment, the acid-generating agent produces acid when irradiated with the first radiation. Furthermore, the acid-generating agent does not produce acid when irradiated with the second radiation instead of the first radiation.

[0145] That is, the acid-producing agent can produce acid when irradiated only by the first radiation. Furthermore, the acid-producing agent can also produce acid when irradiated only by the second radiation after irradiating only the first radiation. However, the acid-producing agent cannot produce acid when irradiated only by the second radiation without irradiating the first radiation.

[0146] That is, an acid-producing agent can generate acid by irradiating the first radiation before the light absorption wavelength changes to absorb the second radiation. On the other hand, an acid-producing agent can generate acid by irradiating the second radiation after the light absorption wavelength changes to absorb the second radiation.

[0147] In the resist composition of this embodiment, the acid-generating agent includes an onium compound that transforms into a carbonyl compound upon irradiation with the first radiation. That is, the acid-generating agent contains an onium compound, which can be transformed into a carbonyl compound by irradiation with only the first radiation. It should be noted that the carbonyl compound can be an onium compound or a compound other than an onium compound.

[0148] In the resist composition of this embodiment, the onium compound contained in the acid-generating agent is not particularly limited.

[0149] Relative to 100 parts by weight of the resist composition components other than the acid-generating agent, the content of the aforementioned acid-generating agent in the resist composition of this embodiment is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 3 to 15 parts by weight.

[0150] In the calculation of the content of the acid-generating agent described above, the organic solvent (solvent) is not included in 100 parts by mass of the resist composition. When the acid-generating agent is contained as a unit in the resin, i.e., when the acid-generating agent is a polymer component, the mass of the polymer backbone is taken as the reference.

[0151] In the resist composition of this embodiment, regardless of the polymer component and the low molecular weight component, two or more of the above-mentioned acid-generating agents can be used alone or in combination, or in combination with other acid-generating agents. Furthermore, in the above-mentioned resist composition, the acid-generating agent can be replaced as part of the polymer component (polymer component).

[0152] Other acid-producing agents besides those containing ononium salts mentioned above include general ionic and nonionic acid-producing agents. Examples of ionic acid-producing agents include ononium salt compounds such as iodonium salts and sulfonium salts, which are not listed above. Examples of nonionic acid-producing agents include N-sulfonyloxyimide compounds, oxime sulfonate compounds, organohalogen compounds, and sulfonyl diazomethane compounds.

[0153] In the case of an acid-generating agent other than the above-mentioned acid-generating agent containing onium salt, its content is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resist composition components other than the total amount of the acid-generating agent.

[0154] The resist composition disclosed herein contains a resist substrate, a compound represented by the above general formulas (4) to (10), and an acid-generating agent (PAG) that generates acid through exposure. If the compound represented by the above general formulas (4) to (6) absorbs ultraviolet light, it changes to the compound represented by the above general formulas (7) to (10), and the absorption wavelength is increased to a longer wavelength, so it can function as a photosensitizer precursor.

[0155] Furthermore, the compounds represented by general formulas (4) to (6) are nonpolar before absorbing ultraviolet light, but become polar after absorbing ultraviolet light, as represented by general formulas (7) to (10). Therefore, by using general formulas (4) to (6) as photosensitizer precursors, the removal of compounds represented by general formulas (7) to (10) becomes easier during a single UV irradiation process after EUV exposure, and an improvement in dissolution contrast can be expected.

[0156] Figure 4 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and the acid-generating agent (PAG) bond). Figure 5 It means Figure 4 The diagram illustrates the activation reaction of the resist composition. (See figure.) Figure 4 As shown, the resist composition of this disclosure preferably has photosensitizer 2 bonded to acid-generating agent (PAG) 3. It should be noted that... Figure 5In the example shown, the nonpolar compound of the above general formula (6) is transformed into the polar compound of the above general formula (9) by absorbing ultraviolet light.

[0157] It should be noted that, Figure 4 In the resist composition shown, the reactivity of each component can be adjusted according to the length of the structure in which photosensitizer 2 and acid-producing agent (PAG) 3 are bonded together.

[0158] It should be noted that, in order to Figure 3 The resist composition shown functions as a photosensitizer chemically amplified resist, preferably in which the resist substrate, acid-generating agent (PAG), and photosensitizer are present in close proximity to each other.

[0159] Therefore, by bonding the photosensitizer to the acid-producing agent (PAG) in this way, the interaction between the photosensitizer and the acid-producing agent (PAG) in the resist composition is increased, and this resist composition containing the photosensitizer and the acid-producing agent can perform high-function as a photosensitizer chemically amplified resist.

[0160] Figure 6 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer bonded to the photoresist substrate). Figures 7-9 It means Figure 6 A figure showing an example of an anti-corrosion composition. Figure 10 It means Figure 7 The diagram shows the reaction of the resist composition to be activated. Figure 11 It means Figure 8 The diagram shows the reaction of the resist composition to be activated. Figure 12 It means Figure 8 A figure showing a specific example of an anti-corrosion composition.

[0161] like Figure 6 As shown, the photosensitive agent 2 in the photoresist composition disclosed herein is preferably bonded to the photoresist substrate 1. It should be noted that... Figures 7-9 The examples shown illustrate three different ways in which the compound represented by the above general formula (6) is bonded to the resist substrate (or resist polymer) 1.

[0162] It should be noted that, Figure 6 In the resist composition shown, the reactivity of each component can be adjusted according to the length of the structure in which the resist substrate 1 and the photosensitizer 2 are bonded together.

[0163] Figure 10 In the example shown, the compound of general formula (6) bonded to the resist substrate 1 is detached from the resist substrate 1 by the absorption of ultraviolet light, generating a polar compound of general formula (9).

[0164] in addition, Figure 11 In the example shown, the compound of general formula (6) bonded to the resist substrate 1 changes to the compound of general formula (9) in a polar state while bonded to the resist substrate 1 through ultraviolet absorption. Figure 11 Specific examples of the examples shown can be listed, for example... Figure 12 The compound shown. It should be noted that, in Figure 12 In this context, MOR stands for metal oxide resist.

[0165] By bonding the photosensitizer to the resist substrate 1 in this way, the interaction between the resist substrate 1, the acid-generating agent (PAG), and the photosensitizer is enhanced when the PAG is present in the vicinity of the resist substrate 1 in the resist composition. Therefore, such a resist composition containing a photosensitizer and a resist substrate can function as a photosensitizer chemically amplified resist with high functionality.

[0166] Figure 13 This is a diagram showing the composition of the photoresist composition (the bonding between the acid-generating agent (PAG) and the photoresist substrate, and the bonding between the photosensitizer and the acid-generating agent (PAG). For example... Figure 13 As shown, the resist composition of this disclosure preferably has an acid-generating agent (PAG) 3 bonded to the resist substrate 1, and the photosensitizer 2 bonded to the acid-generating agent (PAG) 3.

[0167] It should be noted that, Figure 13 In the resist composition shown, the reactivity of each component can be adjusted according to the length of the structure in which the resist substrate 1 is bonded to the acid-generating agent (PAG) 3 and / or the photosensitizer 2 is bonded to the acid-generating agent (PAG) 3.

[0168] Thus, by bonding the acid-generating agent (PAG) 3 to the resist substrate 1, the photosensitizer 2 is also bonded to the acid-generating agent (PAG) 3 in the resist composition, thereby increasing the interaction between the photosensitizer 2 and the acid-generating agent (PAG) 3 in the resist composition. Furthermore, by bonding the acid-generating agent (PAG) 3 to the resist substrate 1, the interaction between the photosensitizer, the acid-generating agent (PAG) 3, and the resist substrate 1 in the resist composition is also increased. Therefore, such a resist composition, in which the acid-generating agent is bonded to the resist substrate and the photosensitizer is bonded to the aforementioned acid-generating agent (PAG), can function as a photosensitizer chemically amplified resist, thus possessing higher functionality.

[0169] The resist composition disclosed herein may contain a resist substrate, at least one compound represented by the above general formulas (4) to (10), an acid-generating agent (PAG), and a quencher (PDB). The compound represented by the above general formulas (4) to (10) is an example of a photosensitizer in the resist composition of the present disclosure containing a quencher.

[0170] Quenchers, also known as photodegradable bases (PDBs), are basic to acids. A quencher is a component that functions by reacting with acids (e.g., neutralizing) to inhibit the formation of acids by acid-producing agents. Furthermore, basicity indicates that it acts as a base relative to an acid. Therefore, basic quenchers are not limited to substances that are basic; they also include weak acid salts that can act as bases relative to acids.

[0171] For example, when the quencher is irradiated with the first type of radiation (radiation with a wavelength of less than 300 nm), it loses its alkalinity to acids. However, when the quencher is irradiated with the second type of radiation (radiation with a wavelength of greater than 300 nm) without irradiation with the first type of radiation, it retains its alkalinity to acids.

[0172] That is, the quencher loses its basicity to acids when irradiated only by the first radiation. Furthermore, the quencher also loses its basicity to acids when irradiated only by the second radiation after irradiating only by the first radiation. Conversely, the quencher retains (does not lose) its basicity to acids when irradiated only by the second radiation without irradiating the first radiation.

[0173] That is, the quencher loses its basicity to acids by being irradiated with the first radiation before the second radiation is absorbed due to a change in the wavelength of light absorption. On the other hand, the quencher loses its basicity to acids by being irradiated with the second radiation after the second radiation is absorbed due to a change in the wavelength of light absorption.

[0174] The quencher is not particularly limited, and can include, for example, ononium compounds that become carbonyl compounds upon irradiation with the first radiation. That is, examples include compounds containing ononium compounds that, upon irradiation with radiation, transform into carbonyl compounds. It should be noted that the carbonyl compound can be an ononium compound or a compound other than an ononium compound.

[0175] Furthermore, there are no particular limitations on the synthesis methods of the above-mentioned onium salts. For example, the synthesis methods of onium salts (maton salts and iodine onium salts) disclosed in International Publication No. WO2018 / 074382 can be used.

[0176] Relative to 100 parts by weight of the resist composition components other than the quencher, the content of the quencher in the resist composition of this embodiment is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, and even more preferably 3 to 15 parts by weight.

[0177] In the calculation of the quencher content above, the organic solvent (solvent) is not included in 100 parts by mass of the resist composition. When the quencher is contained as a unit in the resin, i.e., when the quencher is a polymer component, the mass of the polymer backbone is taken as the reference.

[0178] In the resist composition of this embodiment, regardless of the polymer component and the low molecular weight component, two or more of the above-mentioned quenchers can be used alone or in combination, or in combination with other quenchers. Furthermore, in the above-mentioned resist composition, the quenchers can be replaced as part of the polymer component (polymer component).

[0179] Other quenchers besides those containing ononium salts mentioned above include general ionic and nonionic quenchers. Examples of ionic quenchers include ononium salt compounds such as iodonium salts and sulfonium salts, which are not listed above. Examples of nonionic quenchers include N-sulfonyloxyimide compounds, oxime sulfonate compounds, organohalogen compounds, and sulfonyl diazomethane compounds.

[0180] In the case of a quencher other than the quencher containing onium salts mentioned above, its content is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resist composition components excluding the total amount of the quencher.

[0181] It should be noted that, in addition to the polymer components, acid-generating agents and quenchers described above, the resist composition of this embodiment may also contain a common solvent (organic solvent, etc.), and further include a radiation-sensitive agent, a free radical scavenger, a crosslinking agent, a surfactant, a stabilizer, as well as pigments and other additives.

[0182] The resist composition disclosed herein contains a resist substrate, a compound represented by the above general formulas (4) to (10), an acid-generating agent (PAG) that generates acid by exposure, and a quencher that is alkaline to acid. If the compound represented by the above general formulas (4) to (6) absorbs ultraviolet light, it changes to the compound represented by the above general formulas (7) to (10), and the absorption wavelength is increased to a longer wavelength, so it can function as a photosensitizer precursor.

[0183] Furthermore, the compounds represented by general formulas (4) to (6) are nonpolar before absorbing ultraviolet light, but become polar after absorbing ultraviolet light, as represented by general formulas (7) to (10). Therefore, by using general formulas (4) to (6) as photosensitizer precursors, the removal of compounds represented by general formulas (7) to (10) becomes easier during a single UV irradiation process after EUV exposure, and an improvement in dissolution contrast can be expected.

[0184] Figure 14 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and quencher (PDB) bond). For example... Figure 14 As shown, the resist composition of this disclosure is preferably bonded to photosensitizer 2 and quencher (PDB) 4.

[0185] It should be noted that, in order for the resist composition containing quencher (PDB) to function as a photosensitizer chemically amplified resist, it is preferable that the photosensitizer and quencher (PDB) exist in close proximity in the resist composition.

[0186] It should be noted that, in Figure 14 In the resist composition shown, the reactivity of each component can be adjusted according to the length of the structure in which photosensitizer 2 and quencher (PDB) 4 are bonded together.

[0187] Here, by bonding the photosensitizer and the quencher (PDB) in this way, the interaction between the photosensitizer and the quencher (PDB) in the resist composition is increased. Such a resist composition containing photosensitizer and quencher (PDB) can perform high-performance as a photosensitizer chemically amplified resist.

[0188] Figure 15 , Figure 16 This is a diagram showing the composition of the photoresist composition (the composition of the photosensitizer and the photoresist substrate ion bond).

[0189] In the resist composition disclosed herein, photosensitizer 2 (the compounds represented by the general formulas (4) to (10) above) can be ion-bonded to the resist substrate. The manner of ion bonding is not particularly limited. For example, in... Figure 15 In the example shown, the resist base is anionic, and the photosensitizer is cationic; the two are bonded by Coulomb forces. Figure 16 In the example shown, the resist base is cationic, and the photosensitizer is anionic, and the two are bonded by Coulomb forces.

[0190] By ion-bonding the photosensitizer and the resist base in this way, the removal of the resist base and photosensitizer becomes easier during a single UV irradiation in the post-EUV exposure process, and an improvement in dissolution contrast can be expected.

[0191] Figures 17A-17C This is a diagram illustrating the existing process for chemically amplifying photoresist using photosensitizers. Figures 18A-18C This is a diagram illustrating the process of using a photosensitizer chemically amplified resist with the resist composition disclosed herein.

[0192] It should be noted that, Figures 17A-17C It is to make with Figures 18A-18C The comparison becomes easy with the publicly available diagrams. Figures 17A-17C The configuration of its constituent elements has no particular significance.

[0193] In existing photosensitive chemical amplification resist processes, if an EUV exposure is performed on a resist composition comprising resist substrate 1, photosensitive precursor (PP) 2, acid-generating agent (PAG) 3, and quencher (QC) 4 on substrate B, then the photosensitive precursor (PP) 2 transforms into an activated photosensitive agent (PS) 2′. Figure 17A Next, during development by the developing apparatus E ( Figure 17B Only the exposed portion of the resist composition is removed. Figure 17C ).

[0194] However, in the existing process of chemically amplified photoresist, the activated photoresist (PS)2' of the photoresist precursor (PP)2 is non-polar, and therefore cannot be completely removed by development, which is the main reason for the reduced dissolution contrast.

[0195] In contrast, in the process of using the photosensitive chemical amplification photosensitive agent with the photosensitive composition of this disclosure, by using the compounds shown in the above general formulas (4) to (10) as photosensitizers, when the photosensitive agent precursor (PP)2 is exposed to EUV, the activated photosensitizer (PS)2′ is polar and is therefore removed by development, thus improving the dissolution contrast. Figures 18A-18C ).

[0196] <Method for manufacturing the resist composition>

[0197] Figures 19-21 This is a diagram illustrating a method for manufacturing the resist composition of this disclosure. In the method for manufacturing the resist composition of this disclosure, at least one compound represented by the above general formulas (4) to (10) is mixed into a resist substrate.

[0198] For example, a mixture 6 is prepared by mixing the compounds represented by the above general formulas (4) to (10) as photosensitizers with an anti-corrosion solution in container A. Figure 19 Therefore, the compounds represented by the above general formulas (4) to (10) undergo ion exchange with the resist solution (resist base agent) to obtain... Figure 16 The resist composition shown is a resist base (cationic) and a photosensitizer (anionic) ionically bonded together (mixture 6).

[0199] Furthermore, the method for manufacturing the resist composition (e.g., ion exchange between the resist base and the photosensitizer) can be performed after the formation of the resist substrate. For example, a thin film 6′ in which the photosensitizer is impregnated in the resist substrate can be formed by dropping a solution (photosensitizer 2) of the compound shown in the above general formulas (4) to (10) as a photosensitizer onto the resist substrate (thin film) formed on the substrate B from the nozzle C.

[0200] In the method for manufacturing the resist composition disclosed herein, the resist composition can be obtained by mixing at least one compound represented by general formulas (4) to (10) into the resist substrate, thus making it easy to manufacture the resist composition.

[0201] Furthermore, in the method for manufacturing the resist composition disclosed herein, by performing ion exchange between the resist substrate and at least one compound represented by general formulas (4) to (10), the resulting resist composition becomes a substance formed by ion bonding of the resist base (cation) and the photosensitizer (anion). Therefore, when UV is irradiated once in the process after EUV exposure, a resist composition in which the photosensitizer is easily removed can be obtained.

[0202] <Substrate processing apparatus, substrate processing method>

[0203] Figures 22-25 These figures illustrate one example of a substrate processing apparatus using the resist composition disclosed herein. Figure 22 As shown, the substrate processing apparatus 10 of this disclosure includes: a dark chamber 11, an exposure unit 12, a developing unit 13, and an opening / closing window 14.

[0204] In the substrate processing apparatus 10, the dark chamber 11 is used to hold the substrate B on which a resist film has been formed. The exposure unit 12 exposes the resist composition (a resist composition containing compounds shown in general formulas (4) to (10) as sensitizers) on which the film has been formed on the substrate B. The developing unit 13 develops the exposed resist composition.

[0205] The opening / closing window 14 is closed during exposure and development, and opened when the substrate B enters or leaves the substrate before and after processing. It should be noted that the opening / closing window 14 can be set arbitrarily, and the substrate processing apparatus 10 can also be a structure equipped with an opening / closing window.

[0206] The process in the substrate processing apparatus 10 is not particularly limited, for example, a two-stage exposure lithography process. This photolithography process, such as the resist patterning method, includes: a film formation step, forming a resist film on a substrate using the aforementioned resist composition; a pattern exposure step, irradiating the resist film with a first radiation line (e.g., radiation line having a wavelength of 300 nm or less) through a mask; a one-time exposure step, irradiating the resist film after the pattern exposure step with a second radiation line (e.g., radiation line having a wavelength of greater than 300 nm); a baking step (PEB), heating the resist film after the one-time exposure step; and a step of contacting the resist film after the baking step with a developing solution.

[0207] Furthermore, in the above process, a post-exposure baking (PEB) step, which heats the resist film after the pattern exposure step, can be provided between the pattern exposure step and the one-time exposure step. Alternatively, the baking step (PEB) that heats the resist film after the one-time exposure step can be omitted and replaced with a post-exposure baking (PEB) step.

[0208] Furthermore, in the one-time exposure process, the wavelength of the second radiation (radiation with a wavelength greater than 300 nm) is preferably 350 nm or more, and more preferably 390 nm or more. It should be noted that there is no particular upper limit to the wavelength of the second radiation. From the viewpoint that the absorption wavelength peak of the compounds represented by the compounds represented by the above general formulas (4) to (10) after activation is around 350 nm to 400 nm, it is preferably 500 nm or less, and more preferably 450 nm or less.

[0209] The process in such a substrate processing apparatus 10 is an example of the substrate processing method disclosed herein.

[0210] In the substrate processing apparatus of this disclosure, a resist composition containing compounds represented by the above general formulas (4) to (10) as sensitizers is used. However, the compounds represented by the above general formulas (4) to (6) change to the compounds represented by the above general formulas (7) to (10) by absorbing ultraviolet light, thus increasing the absorption wavelength. Therefore, if the compounds represented by the above general formulas (4) to (10) are exposed to visible light (short-wavelength visible light) close to ultraviolet light, they may be unintentionally activated. Therefore, in the substrate processing apparatus of this disclosure, such unintentional activation can be prevented by performing exposure and development based on ultraviolet irradiation in a dark chamber.

[0211] Furthermore, in the substrate processing method disclosed herein, a resist composition containing the compounds shown in the above general formulas (4) to (10) is used. However, as described above, the compounds shown in the above general formulas (4) to (6) (compounds having a tonne structure, an acridine structure, or anthracene structure) change to the compounds shown in the above general formulas (7) to (10) respectively by absorbing ultraviolet light, and the absorption wavelength becomes longer. Therefore, by using the compounds shown in the above general formulas (4) to (6) as photosensitizer precursors, the photosensitizer that changes to the compounds shown in the above general formulas (7) to (10) can be treated with ultraviolet light close to visible light when irradiating UV light once in the process after EUV exposure.

[0212] In addition, as mentioned above, the compounds shown in general formulas (4) to (6) are non-polar before absorbing ultraviolet light, but become polar after absorbing ultraviolet light. Therefore, when UV is irradiated once in the process after EUV exposure, the removal of the compounds shown in general formulas (7) to (10) becomes easier, and an improvement in dissolution contrast can be expected.

[0213] like Figure 23 As shown, the substrate processing apparatus 20 of this disclosure includes an infrared monitor. The type of infrared monitor is not particularly limited; for example, it can be composed of an infrared lamp 24 and an infrared camera 25. The infrared monitor (infrared lamp 24 and infrared camera 25) is installed inside a darkroom 21 and can monitor the interior of the darkroom 21.

[0214] As described above, the compounds represented by the above general formulas (4) to (10) included as sensitizers in the resist composition may be unintentionally activated when exposed to visible light (short-wavelength visible light) close to ultraviolet light. Therefore, in the substrate processing apparatus 20 of this disclosure, by providing an infrared monitor in a dark room, exposure caused by short-wavelength visible light can be prevented, and the substrate processing can also be monitored in such a dark room.

[0215] like Figure 24 As shown, the substrate processing apparatus 30 of this disclosure includes a coating section 31, a flow path 32, and a nozzle 33. The coating section 31 is a spin coater for fixing a substrate B coated with a resist composition.

[0216] Flow path 32 supplies the flow of the resist composition. Flow path 32 consists of flow path 32A and a branch flow path 32B. The resist solution flows in flow path 32A, and the potential photosensitizer (photosensitizer precursor) solution flows in flow path 32B. In flow path 32, the resist solution flowing in flow path 32A mixes with the potential photosensitizer (photosensitizer precursor) solution flowing in flow path 32B. It should be noted that the configuration of flow path 32 is not limited to this; it can also be that the potential photosensitizer (photosensitizer precursor) solution flows in flow path 32A, and the resist solution flows in flow path 32B, etc.

[0217] Nozzle 33 is disposed above coating section 31 and communicates with front end of flow path 32. In substrate processing apparatus 30 of this disclosure, resist composition mixed in flow path 32 is ejected from nozzle 33 and coated onto substrate B. Thus, the above-described method for manufacturing resist composition (mixing at least one compound shown in general formulas (4) to (10) into resist substrate) can be implemented.

[0218] like Figure 25As shown, the substrate processing apparatus 40 of this disclosure has a flow path 42 and a nozzle 43. The flow path 42 is composed of a flow path 42A and a branch flow path 42B. The flow path 42A communicates with the nozzle 43 and allows the flow of a resist composition (resist solution and potential photosensitizer solution). The flow path 42A is an example of a first flow path in the substrate processing apparatus of this disclosure.

[0219] Flow path 42B is connected to flow path 42A and supplies alkaline solution flow. Flow path 42B is an example of a second flow path in the substrate processing apparatus of this disclosure. To displace (neutralize) acid remaining in flow path 42, the alkaline solution flows within flow path 42 before the resist composition flows. Furthermore, after the alkaline solution has flowed, rinsing with deionized water (DIW) is preferred.

[0220] Nozzle 43 is connected to the front end of flow path 42A and sprays out the resist composition. Nozzle 43 is an example of a nozzle in the substrate processing apparatus of this disclosure.

[0221] In the substrate processing apparatus 40 of this disclosure, since the resist composition flowing in the flow path 42 contains a potentially acid-intolerant photosensitizer solution, the resist composition may deteriorate due to the presence of acid in the flow path 42. Therefore, in the substrate processing apparatus 40 of this disclosure, by providing a second flow path (flow path 42B) that is connected to the second flow path (flow path 42A) and supplies alkaline solution, the resist composition is allowed to flow after the flow path 42 has been pre-displaced with alkaline solution, thereby preventing the resist composition from deteriorating due to acid.

[0222] The above-disclosed implementation methods include, for example, the following.

[0223] (Note 1)

[0224] A resist composition comprising at least one compound represented by the following general formulas (11), (12) and (13),

[0225]

[0226] In general formula (11), R1 to R4 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted).

[0227] X1 and Y1 are each independently selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

[0228]

[0229] In general formula (12), R5 to R9 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0230] X2 can be any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom.

[0231] Y2 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0232]

[0233] In general formula (13), R 10 ~R 15 Each of the following is independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0234] X3 can be any one of the following groups: carbon atoms, silicon atoms, germanium atoms, and tin atoms.

[0235] Y3 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0236] (Note 2)

[0237] An anti-corrosion composition comprising a compound represented by the following general formula (14).

[0238]

[0239] In general formula (14), R1 to R4 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted).

[0240] X1 and Y1 are each independently selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

[0241] (Note 3)

[0242] An anti-corrosion composition comprising a compound represented by the following general formula (15).

[0243]

[0244] In general formula (15), R5 to R9 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0245] X2 can be any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom.

[0246] Y2 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0247] (Note 4)

[0248] An anti-corrosion composition comprising a compound represented by the following general formula (16).

[0249]

[0250] In general formula (16), R5 to R9 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0251] Y2 is selected from any one of the following groups: oxygen, sulfur, selenium, and tellurium atoms.

[0252] (Note 5)

[0253] An anti-corrosion composition comprising a compound represented by the following general formula (17).

[0254]

[0255] In general formula (17), R1 to R3 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted).

[0256] X1 is an oxygen atom or a sulfur atom.

[0257] (Note 6)

[0258] An anti-corrosion composition comprising a compound represented by the following general formula (18).

[0259]

[0260] In general formula (18), R5 to R8 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0261] X2 can be any one of the following groups: nitrogen, phosphorus, arsenic, and antimony atoms.

[0262] (Note 7)

[0263] An anti-corrosion composition comprising a compound represented by the following general formula (19).

[0264]

[0265] [In general formula (19), R5 to R8 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either linear, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either linear, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted).]

[0266] (Note 8)

[0267] An anti-corrosion composition comprising a compound represented by the following general formula (20).

[0268]

[0269] In general formula (20), R 10 ~R 14 Each of the following is independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups.

[0270] X3 can be any one of the following groups: carbon, silicon, germanium, and tin atoms.

[0271] (Note 9)

[0272] The resist composition according to any one of Appendices 1 to 8 comprises: a resist substrate; at least one compound represented by the general formulas (11) to (20); and an acid-generating agent that generates acid by exposure.

[0273] (Postscript 10)

[0274] According to Appendix 9, the resist composition is wherein the compound is bonded to the acid-producing agent.

[0275] (Postscript 11)

[0276] According to Appendix 9 or 10, the resist composition wherein the compound is bonded to the resist substrate.

[0277] (Postscript 12)

[0278] According to any one of Appendices 9 to 11, the resist composition wherein the acid-generating agent is bonded to the resist substrate and the compound is bonded to the acid-generating agent.

[0279] (Postscript 13)

[0280] The resist composition according to any one of Appendices 1 to 12 comprises: a resist substrate; at least one compound represented by the general formulas (11) to (20); an acid-generating agent that generates acid by exposure; and a quencher that is alkaline to acid.

[0281] (Postscript 14)

[0282] According to the resist composition described in Appendix 13, wherein the compound is bonded to the quencher.

[0283] (Postscript 15)

[0284] The resist composition according to any one of Appendices 9 to 14, wherein the compound is ionically bonded to the resist substrate.

[0285] (Postscript 16)

[0286] A method for manufacturing a resist composition, wherein at least one compound represented by the general formula (11) to (20) is mixed in a resist substrate.

[0287] (Postscript 17)

[0288] According to the method for manufacturing the resist composition described in Appendix 16, ion exchange is performed between the resist substrate and the compound.

[0289] (Postscript 18)

[0290] A substrate processing apparatus comprising:

[0291] A darkroom, used to hold substrates in place;

[0292] An exposure unit, disposed in the dark chamber, exposes the resist composition described in any one of Appendices 1 to 15, on which a film is formed on the substrate; and

[0293] The developing unit, which is located in the dark chamber, develops the exposed resist composition.

[0294] (Postscript 19)

[0295] The substrate processing apparatus according to Appendix 18 has the following features:

[0296] A nozzle that sprays the corrosion resist composition;

[0297] A first flow path, which communicates with the nozzle, for the flow of the resist composition; and

[0298] The second flow path is connected to the first flow path and supplies the alkaline solution to flow through it.

[0299] (Postscript 20)

[0300] A substrate processing method, comprising:

[0301] The film forming process forms a resist film comprising the resist composition described in any one of Appendices 1 to 15 on a substrate;

[0302] In the pattern exposure process, the resist film is irradiated with radiation having a wavelength of less than 300 nm through a mask;

[0303] A one-time exposure process irradiates the resist film after the pattern exposure process with radiation having a wavelength greater than 300 nm;

[0304] The baking process involves heating the resist film after the one-time exposure process; and

[0305] The process of bringing the resist film after the baking process into contact with the developing solution.

[0306] The embodiments of this disclosure have been described above, but this disclosure is not limited to these embodiments, and various modifications and alterations can be made within the scope of the disclosure as described in the claims.

[0307] This application claims priority based on Japanese Patent Application No. 2023-169727, filed on September 29, 2023, the entire contents of which are incorporated herein by reference.

[0308] Explanation of reference numerals in the attached figures

[0309] 1. Resist substrate

[0310] 2. Photosensitizer (photosensitizer precursor)

[0311] 2′ Photosensitizer (activated photosensitizer)

[0312] 3. Acid-generating agent (PAG)

[0313] 4. Catalyst (PDB)

[0314] B substrate

[0315] E Developing apparatus

[0316] A container

[0317] C Exit

[0318] 6. Mixture

[0319] 6′ film

[0320] 10, 20, 30, 40 Substrate processing apparatus

[0321] 11.21 Darkroom

[0322] 12, 22 Exposure Department

[0323] 13, 23 Developing Department

[0324] 14 Opening and closing windows

[0325] 24 Infrared lights

[0326] 25 Infrared cameras

[0327] Coating sections 31 and 41

[0328] 32, 32A, 32B, 42, 42A, 42B flow path

[0329] Nozzles 33 and 43

Claims

1. A resist composition comprising at least one compound represented by the following general formulas (1), (2) and (3), In general formula (1), R1 to R4 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X1 and Y1 are each independently selected from any one of the groups consisting of oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms. In general formula (2), R5 to R9 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X2 can be any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom. Y2 can be selected from any one of the following groups: oxygen atom, sulfur atom, selenium atom, and tellurium atom. In general formula (3), R 10 ~R 15 Each of the following is independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups. X3 can be any one of the following groups: carbon atoms, silicon atoms, germanium atoms, and tin atoms. Y3 is selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

2. A resist composition comprising a compound represented by the following general formula (4), In general formula (4), R1 to R4 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X1 and Y1 are each independently selected from any one of the groups consisting of oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms.

3. A resist composition comprising a compound represented by the following general formula (5), In general formula (5), R5 to R9 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X2 can be any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom. Y2 is selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

4. A resist composition comprising a compound represented by the following general formula (6), In general formula (6), R5 to R9 are each independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms that has substituted groups; an alkenyl group with 1 to 12 carbon atoms that has substituted groups; an aryl group with 6 to 14 carbon atoms that has substituted groups; and a heteroaryl group with 4 to 12 carbon atoms that has substituted groups. Y2 is selected from any one of the groups consisting of oxygen, sulfur, selenium, and tellurium atoms.

5. A resist composition comprising a compound represented by the following general formula (7), In general formula (7), R1 to R3 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X1 is an oxygen atom or a sulfur atom.

6. A resist composition comprising a compound represented by the following general formula (8), In general formula (8), R5 to R8 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an alkenyl group having 1 to 12 carbon atoms (either straight-chain, branched, or cyclic); an aryl group having 6 to 14 carbon atoms (either substituted); and a heteroaryl group having 4 to 12 carbon atoms (either substituted). X2 is any one of the following groups: nitrogen atom, phosphorus atom, arsenic atom, and antimony atom.

7. A resist composition comprising a compound represented by the following general formula (9), In general formula (9), R5 to R8 are each independently selected from any one of the following groups: an alkyl group having 1 to 12 carbon atoms that is either straight-chain, branched, or cyclic with substituents; an alkenyl group having 1 to 12 carbon atoms that is either straight-chain, branched, or cyclic with substituents; an aryl group having 6 to 14 carbon atoms that is either substituents; and a heteroaryl group having 4 to 12 carbon atoms that is either substituents.

8. A resist composition comprising a compound represented by the following general formula (10), In general formula (10), R 10 ~R 14 Each of the following is independently selected from any one of the following groups: a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms with substituted groups; an alkenyl group having 1 to 12 carbon atoms with substituted groups; an aryl group having 6 to 14 carbon atoms with substituted groups; and a heteroaryl group having 4 to 12 carbon atoms with substituted groups. X3 is any one of the groups consisting of carbon atoms, silicon atoms, germanium atoms, and tin atoms.

9. The resist composition according to any one of claims 1 to 8, comprising: Resist substrate; At least one compound represented by the general formulas (1) to (10); and Acid-producing agents that generate acid through exposure.

10. The resist composition according to claim 9, wherein, The compound is bonded to the acid-producing agent.

11. The resist composition according to claim 9, wherein, The compound is bonded to the resist substrate.

12. The resist composition according to claim 9, wherein, The acid-generating agent is bonded to the resist substrate. The compound is bonded to the acid-producing agent.

13. The resist composition according to any one of claims 1 to 8, comprising: Resist substrate; At least one compound represented by the general formulas (1) to (10); Acid-producing agents that generate acid through exposure; as well as A quencher that is alkaline to acid.

14. The resist composition according to claim 13, wherein, The compound is bonded to the quencher.

15. The resist composition according to claim 9, wherein, The compound is ionicly bonded to the resist substrate.

16. A method for manufacturing a resist composition, comprising the method for manufacturing the resist composition according to any one of claims 1 to 8, wherein, At least one of the compounds represented by the general formulas (1) to (10) is mixed into the resist substrate.

17. The method for manufacturing the resist composition according to claim 16, wherein, Ion exchange is performed between the resist substrate and the compound.

18. A substrate processing apparatus comprising: A darkroom, used to hold substrates in place; An exposure unit, disposed in the dark chamber, exposes the resist composition of any one of claims 1 to 8, which has a film formed on the substrate, to the substrate; and The developing unit, which is located in the dark chamber, develops the exposed resist composition.

19. The substrate processing apparatus according to claim 18, comprising: A nozzle that sprays the corrosion resist composition; A first flow path, which communicates with the nozzle, for the flow of the resist composition; and The second flow path is connected to the first flow path and supplies the alkaline solution to flow through it.

20. A substrate processing method, comprising: The film forming process involves forming a resist film comprising the resist composition according to any one of claims 1 to 8 on a substrate; In the pattern exposure process, the resist film is irradiated with radiation having a wavelength of less than 300 nm through a mask; A one-time exposure process irradiates the resist film after the pattern exposure process with radiation having a wavelength greater than 300 nm; The baking process involves heating the resist film after the one-time exposure process; and The process of bringing the resist film after the baking process into contact with the developing solution.

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