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

Abstract

A resist composition according to the present invention contains at least one of compounds represented by general formulas (1), (2), and (3).

Description

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

[0001] The present disclosure relates to a resist composition, a method for producing a resist composition, a substrate processing apparatus, and a substrate processing method.

[0002] Photosensitizer chemically amplified resist (PSCAR) for EUV exposure has a photoacid generator that generates acid when it absorbs EUV light, and a photosensitizer that is activated by the acid and changes to absorb light. In the PSCAR process, the photoacid generator is exposed to EUV light, and the photosensitizer activated by the generated acid absorbs EUV light, and further acid is generated from the photoacid generator through energy transfer, etc.

[0003] Patent Document 1 discloses a technology in which a compound that changes from an acetal structure to a ketone structure in response to an external stimulus (light, acid, etc.) is used as a photosensitizer precursor for use in a PSCAR process for EUV exposure.

[0004] JP 2018-188458 A

[0005] In conventional technology, when a photosensitizer precursor changes from an acetal structure to a ketone structure, the conjugated range is extended and the absorption wavelength becomes longer, but there is no change in polarity, so there is no significant difference in solubility during development, and sufficient dissolution contrast cannot be obtained.

[0006] An object of the present disclosure is to provide a resist composition that can improve dissolution contrast.

[0007] A resist composition according to one embodiment of the present disclosure contains at least one compound represented by the following general formulas (1), (2), and (3). [In general formula (1), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y１ are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (2), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (3), R １０ ~R １５ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom; ３ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0008] According to one aspect of the present disclosure, a resist composition capable of improving dissolution contrast is obtained.

[0009] 7 is a graph showing the absorption wavelength of a photosensitizer (photosensitizer precursor) used in a resist composition before activation. It is a graph showing the absorption wavelength of the photosensitizer in FIG. 1 after activation. It is a diagram showing the composition of a resist composition. It is a diagram showing the composition of a resist composition (a composition in which a photosensitizer bonds to an acid generator (PAG)). It is a diagram showing a reaction in which the resist composition of FIG. 4 is activated. It is a diagram showing the composition of a resist composition (a composition in which a photosensitizer bonds to a resist base material). It is a diagram showing an example of the resist composition of FIG. 6. It is a diagram showing an example of the resist composition of FIG. 6. It is a diagram showing an example of the resist composition of FIG. 6. It is a diagram showing a reaction in which the resist composition of FIG. 7 is activated. It is a diagram showing a reaction in which the resist composition of FIG. 8 is activated. It is a diagram showing a specific example of the resist composition of FIG. 8. It is a diagram showing the composition of a resist composition (a composition in which an acid generator (PAG) bonds to a resist base material, and a photosensitizer bonds to the acid generator (PAG)). It is a diagram showing the composition of a resist composition (a composition in which a photosensitizer bonds to a quencher (PDB)). It is a diagram showing the composition of a resist composition (a composition in which a photosensitizer ionically bonds to a resist base material). FIG. 1 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is ionically bonded to a resist base material). FIG. 2 is a diagram showing a process for a conventional photosensitizer chemically amplified resist. FIG. 3 is a diagram showing a process for a conventional photosensitizer chemically amplified resist. FIG. 4 is a diagram showing a process for a conventional photosensitizer chemically amplified resist. FIG. 5 is a diagram showing a process for a photosensitizer chemically amplified resist using a resist composition of the present disclosure. FIG. 6 is a diagram showing a process for a photosensitizer chemically amplified resist using a resist composition of the present disclosure. FIG. 7 is a diagram showing an embodiment of producing a resist composition of the present disclosure. FIG. 8 is a diagram showing an embodiment of producing a resist composition of the present disclosure. FIG. 9 is a diagram showing an embodiment of producing a resist composition of the present disclosure. FIG. 10 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure. FIG. 11 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure.

[0010] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. Note that common parts in the drawings may be denoted by the same or corresponding reference numerals, and descriptions thereof may be omitted.

[0011] <Resist Composition> The resist composition of the present disclosure contains at least one compound represented by the following general formulas (4), (5), and (6). These compounds can function as a photosensitizer (or a precursor of a photosensitizer) in the resist composition.

[0012] The compound represented by the general formula (1) contains a heterocyclic ring in which three six-membered rings are fused together. １３ H １０ X １ (However, X １ are elements of Group 16 of the Periodic Table excluding Po) (hereinafter, this may be referred to as a xanthylium skeleton or a xanthylium structure).

[0013] In general formula (1), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y １ are each independently any one selected from the group consisting of an oxygen (O) atom, a sulfur (S) atom, a selenium (Se) atom, and a tellurium (Te) atom.

[0014] In the compound represented by general formula (1), examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornan-1-yl group, and a norbornan-2-yl group.

[0015] Examples of the optionally substituted linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms include the above-mentioned alkyl groups in which at least one carbon-carbon single bond is substituted with a carbon-carbon double bond.

[0016] Examples of the aryl group having 6 to 14 carbon atoms which may have a substituent include monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups in which at least two such monocyclic aromatic hydrocarbon rings are fused together.

[0017] Examples of the optionally substituted heteroaryl group having 4 to 12 carbon atoms include those containing at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom in place of at least one carbon atom of the above-mentioned aryl group.

[0018] Among these, the compound represented by the general formula (1) is １ is preferably an oxygen atom or a sulfur atom, and X １ is more preferably an oxygen atom.

[0019] The compound represented by the general formula (2) contains a heterocyclic ring C １３ H １０ X ２ (However, X ２ is a Group 15 element of the Periodic Table excluding Bi) (hereinafter, this may be referred to as an acridinium skeleton or an acridinium structure).

[0020] In general formula (2), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen (N) atom, a phosphorus (P) atom, an arsenic (As) atom, and an antimony (Sb) atom; Y ２is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0021] In the compound represented by general formula (2), examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornan-1-yl group, and a norbornan-2-yl group.

[0022] Examples of the optionally substituted linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms include the above-mentioned alkyl groups in which at least one carbon-carbon single bond is substituted with a carbon-carbon double bond.

[0023] Examples of the aryl group having 6 to 14 carbon atoms which may have a substituent include monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups in which at least two such monocyclic aromatic hydrocarbon rings are fused together.

[0024] Examples of the optionally substituted heteroaryl group having 4 to 12 carbon atoms include those containing at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom in place of at least one carbon atom of the above-mentioned aryl group.

[0025] Among these, the compound represented by the general formula (2) is ２ is preferably a nitrogen atom or a phosphorus atom, and X ２ is more preferably a nitrogen atom.

[0026] The compound represented by the general formula (3) contains a heterocyclic ring in which three six-membered rings are fused together. １３ H １０ X ３ (However, X ３ is a Group 14 element of the Periodic Table excluding Pb) (hereinafter, this may be referred to as an anthracene skeleton or an anthracene structure).

[0027] In addition, in the general formula (3), R１０ ~R １５ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon (C) atom, a silicon (Si) atom, a germanium (Ge) atom, and a tin (Sn) atom; Y ３ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0028] In the compound represented by general formula (3), examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms which may have a substituent include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isopropyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantan-1-yl group, an adamantan-2-yl group, a norbornan-1-yl group, and a norbornan-2-yl group.

[0029] Examples of the optionally substituted linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms include the above-mentioned alkyl groups in which at least one carbon-carbon single bond is substituted with a carbon-carbon double bond.

[0030] Examples of the aryl group having 6 to 14 carbon atoms which may have a substituent include monocyclic aromatic hydrocarbon groups and fused polycyclic aromatic hydrocarbon groups in which at least two such monocyclic aromatic hydrocarbon rings are fused together.

[0031] Examples of the optionally substituted heteroaryl group having 4 to 12 carbon atoms include those containing at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom in place of at least one carbon atom of the above-mentioned aryl group.

[0032] Among these, the compound represented by the general formula (3) is３ is preferably a carbon atom or a silicon atom, and X ３ is more preferably a silicon atom.

[0033] The resist composition of the present disclosure may contain a compound represented by the following general formula (7): The compound represented by general formula (7) is a compound obtained by activating the compound represented by general formula (1) above by absorbing ultraviolet light.

[0034] In general formula (7), R １ ~R ３ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ is an oxygen atom or a sulfur atom.

[0035] The compound represented by the general formula (7) is common to the compound represented by the general formula (1) in that it has a xanthylium skeleton, and ４ -Y １ The difference is that the - is a cation having a polarity that has been eliminated.

[0036] The resist composition of the present disclosure may contain a compound represented by the following general formula (8) obtained by activating the compound represented by the above general formula (2). In general formula (8), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom.

[0037] The compound represented by the general formula (8) is common to the compound represented by the general formula (2) in that it has an acridinium skeleton, and the 5-position (X ２ ) to R ６ is eliminated, and R is released from the 10-position of the acridinium skeleton. ９ -Y ２ It differs in that the - is a polar cation that has been eliminated.

[0038] The compound represented by the general formula (8) is preferably X ２ is a nitrogen atom, that is, a compound represented by the following general formula (9):

[0039] In general formula (9), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group of 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group of 1 to 12 carbon atoms; an optionally substituted aryl group of 6 to 14 carbon atoms; and an optionally substituted heteroaryl group of 4 to 12 carbon atoms.

[0040] The resist composition of the present disclosure may contain a compound represented by general formula (3). The compound represented by general formula (3) is a compound represented by the following general formula (10) that is activated by absorbing ultraviolet light.

[0041] In general formula (10), R １０ ~R １４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom.

[0042] The compound represented by the general formula (10) is common to the compound represented by the general formula (3) in that it has an anthracene skeleton, and the 5-position (X ３ ) to R １１ is eliminated, and R is released from the 10th position of the anthracene skeleton. １５ -Y ３ The compound represented by general formula (10) is weakly cationic, with a slight bias (polarity) of electrons at the 5-position of the anthracene skeleton.

[0043] Fig. 1 is a graph showing the absorption wavelength of a photosensitizer precursor (a compound represented by the above general formulas (1) and (2)) used in a resist composition of the present disclosure before the photosensitizer precursor absorbs ultraviolet light (before activation). Fig. 2 is a graph showing the absorption wavelength of a photosensitizer (a compound represented by the above general formulas (7) and (8)) after the photosensitizer precursor (a compound represented by the above general formulas (1) and (2)) in Fig. 1 absorbs ultraviolet light (after activation).

[0044] In Figure 1, the photosensitizer precursor before absorbing UV light (before activation) has an absorption wavelength peak at around 250 nm to 300 nm, whereas in Figure 2, the photosensitizer after the photosensitizer precursor absorbs UV light (after activation) has an absorption wavelength peak at around 350 nm to 400 nm.

[0045] That is, it is expected that the compounds represented by the above general formulas (4) to (6) (compounds having a xanthylium structure, an acridinium structure, or an anthracene structure) will change to the compounds represented by the above general formulas (7) to (10) by absorbing ultraviolet light, respectively, and that the absorption wavelength will become longer. For this reason, by using the compounds represented by the above general formulas (4) to (6), etc. as photosensitizer precursors, the photosensitizers converted to the compounds represented by the above general formulas (7) to (10) can be treated with ultraviolet light close to visible light when irradiated with UV all at once in the process after EUV exposure.

[0046] Furthermore, the compounds represented by the general formulas (4) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change into the polar compounds represented by the general formulas (7) to (10), respectively. Therefore, when UV light is irradiated all at once in the process after EUV exposure, the compounds represented by the general formulas (7) to (10) can be easily removed, and improvement in dissolution contrast can be expected.

[0047] 3 is a diagram showing the composition of a resist composition. The resist composition of the present disclosure is a composition containing a resist base material 1 and a photosensitizer 2, and may also contain an acid generator 3.

[0048] The resist base material 1 represents a polymer component that becomes soluble or insoluble in a developer by the action of an acid. The polymer represents a compound (polymer) obtained by polymerizing two or more monomers, including a copolymer obtained by polymerizing two or more types of monomers. The action of the acid represents at least one of the cases where the acid functions as a reactant or the case where the acid functions as a catalyst.

[0049] The polymer component is not particularly limited, and examples thereof include a first polymer (hereinafter also referred to as "polymer [A]") having a structural unit (hereinafter also referred to as "structural unit (I)") containing a group that generates a polar group upon the action of an acid (hereinafter also referred to as "acid-dissociable group"). Furthermore, the polymer component may further contain a second polymer (hereinafter also referred to as "polymer [B]") that does not contain structural unit (I) as a polymer component other than the polymer component.

[0050] The polymer [A] or the polymer [B] may further include a structural unit containing a fluorine atom (hereinafter also referred to as "structural unit (II)"), a structural unit (III) containing a phenolic hydroxyl group, and a structural unit (IV) containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof, or may further include other structural units other than the structural units (I) to (IV).

[0051] The polymer [A] may further have the structural units (II) to (IV) or other structural units. The polymer [B] is a polymer different from the polymer [A]. The polymer [B] preferably has the structural unit (II), and may have structural units (III) and (IV) or other structural units other than the structural units (III) to (IV).

[0052] The lower limit of the content of the structural unit (I) relative to all structural units constituting the polymer [A] is preferably 10 mol%, more preferably 20 mol%, even more preferably 25 mol%, and particularly preferably 30 mol%. Meanwhile, the upper limit of this content is preferably 80 mol%, more preferably 70 mol%, even more preferably 65 mol%, and particularly preferably 60 mol%. By setting the content within this range, it is possible to ensure sufficient dissolution contrast in a developer between the pattern-exposed and non-exposed areas of the resist composition film formed from the resist composition, thereby improving resolution and the like.

[0053] When the polymer [A] has the structural unit (II), the lower limit of the content of the structural unit (II) relative to all structural units constituting the 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 content is preferably 40 mol%, more preferably 35 mol%, and even more preferably 30 mol%. By setting the content within the above range, sensitivity is further improved when EUV or the like is used as pattern exposure light. On the other hand, if the content exceeds the above upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be reduced.

[0054] When the polymer component contains a [B] polymer and the [B] polymer has a structural unit (II), the lower limit of the structural unit (II) relative to all structural units constituting the [B] polymer is preferably 3 mol%, more preferably 5 mol%, and even more preferably 10 mol%. On the other hand, the upper limit of the content is preferably 40 mol%, more preferably 35 mol%, and even more preferably 30 mol%. By setting the content within the above range, sensitivity can be further improved when EUV or the like is used as pattern exposure light. On the other hand, if the content exceeds the above upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be reduced.

[0055] When the polymer (A) or the polymer (B) has the structural unit (III), the sensitivity can be further improved when irradiated with KrF excimer laser light, EUV (extreme ultraviolet), electron beam, or the like in the patterned exposure step described below.

[0056] When the polymer [A] has the structural unit (III), the lower limit of the content of the structural unit (III) relative to all structural units constituting the polymer [A] is preferably 1 mol%, more preferably 30 mol%, and even more preferably 50 mol%. Meanwhile, the upper limit of this content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 75 mol%. By setting the content of the structural unit (III) within this range, the sensitivity of the resist composition can be further improved.

[0057] When the polymer component contains the polymer [B] and the polymer [B] has the structural unit (III), the lower limit of the content of the structural unit (III) relative to all structural units constituting the 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 content is preferably 90 mol%, more preferably 80 mol%, and even more preferably 75 mol%. By setting the content of the structural unit (III) within the above range, the sensitivity of the resist composition can be further improved.

[0058] The structural unit (III) can be formed by, for example, polymerizing a monomer in which the hydrogen atom of an —OH group in an aromatic ring containing a phenolic hydroxyl group is substituted with an acetyl group or the like, and then subjecting the resulting polymer to a hydrolysis reaction in the presence of an amine.

[0059] By further including the structural unit (IV), the polymer [A] and the polymer [B] can adjust the solubility in a developer to a more appropriate level, thereby further improving the lithography performance of the resist composition. The adhesiveness between a resist composition film formed from the resist composition and a substrate can be improved. Here, the lactone structure refers to a structure having one ring (lactone ring) containing a group represented by —O—C(O)—. The cyclic carbonate structure refers to a structure having one ring (cyclic carbonate ring) containing a group represented by —O—C(O)—O—. The sultone structure refers to a structure having one ring (cyclic carbonate ring) containing a group represented by —O—S(O) ２ - refers to a structure having one ring (sultone ring) containing a group represented by the formula:

[0060] As the structural unit (IV), a structural unit containing a norbornane lactone structure, a structural unit containing an oxanorbornane lactone structure, a structural unit containing a γ-butyrolactone structure, a structural unit containing an ethylene carbonate structure, and a structural unit containing a norbornane sultone structure are preferred, and structural units derived from norbornane lactone-yl (meth)acrylate, structural units derived from oxanorbornane lactone-yl (meth)acrylate, structural units derived from cyano-substituted norbornane lactone-yl (meth)acrylate, structural units derived from norbornane lactone-yloxycarbonylmethyl (meth)acrylate, structural units derived from butyrolactone-3-yl (meth)acrylate, butyrolactone- More preferred are structural units derived from 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)cyclohexan-1-yl(meth)acrylate, structural units derived from ethylene carbonate-ylmethyl(meth)acrylate, structural units derived from cyclohexene carbonate-ylmethyl(meth)acrylate, structural units derived from norbornane sultone-yl(meth)acrylate, and structural units derived from norbornane sultone-yloxycarbonylmethyl(meth)acrylate.

[0061] When the polymer [A] has the structural unit (IV), the lower limit of the content of the structural unit (IV) relative to all structural units constituting the polymer [A] is preferably 1 mol%, more preferably 10 mol%, even more preferably 20 mol%, and particularly preferably 25 mol%. On the other hand, the upper limit of the content is preferably 70 mol%, more preferably 65 mol%, even more preferably 60 mol%, and particularly preferably 55 mol%. By setting the content within the above range, it is possible to further improve the adhesion between a resist film formed from the resist composition and a substrate.

[0062] When the polymer component contains the polymer [B] and the polymer [B] has the structural unit (IV), the lower limit of the content of the structural unit (IV) relative to all structural units constituting the polymer [B] is preferably 1 mol%, more preferably 10 mol%, even more preferably 20 mol%, and particularly preferably 25 mol%. On the other hand, the upper limit of the content is preferably 70 mol%, more preferably 65 mol%, even more preferably 60 mol%, and particularly preferably 55 mol%. By setting the content within the above range, the adhesion between the resist film formed from the resist composition and the substrate can be further improved.

[0063] [Other Structural Units] The polymer [A] and the polymer [B] may have other structural units in addition to the structural units (I) to (IV). Examples of the other structural units include structural units containing a polar group and structural units containing a non-dissociable hydrocarbon group. Examples of the polar group include an alcoholic hydroxyl group, a carboxy group, a cyano group, a nitro group, and a sulfonamide group. Examples of the non-dissociable hydrocarbon group include a linear alkyl group. The upper limit of the content of the other structural units relative to all structural units constituting the polymer [A] is preferably 20 mol %, more preferably 10 mol %.

[0064] The lower limit of the combined amount of the polymer (A) and the polymer (B) is preferably 70 mass %, more preferably 75 mass %, and even more preferably 80 mass %, of the total solid content of the resist composition, where "total solid content" refers to all components of the resist composition other than the solvent.

[0065] The weight average molecular weight (Mw) of the polymer [A] in terms of polystyrene standards, as determined by gel permeation chromatography (GPC), is not particularly limited, but the lower limit is preferably 1,000, more preferably 2,000, even more preferably 3,000, and particularly preferably 5,000. On the other hand, the upper limit of the Mw of the polymer [A] is preferably 50,000, more preferably 30,000, even more preferably 20,000, and particularly preferably 15,000.

[0066] By setting the Mw of the polymer [A] within the above range, the coatability and development defect suppression of the resist composition are improved. If the Mw of the polymer [A] is below the above lower limit, a resist film having sufficient heat resistance may not be obtained. Conversely, if the Mw of the polymer [A] is above the above upper limit, the developability of the resist film may be reduced.

[0067] The lower limit of the ratio (Mw / Mn) of the Mw of the polymer (A) to the polystyrene-equivalent number average molecular weight (Mn) determined by GPC is usually 1. On the other hand, the upper limit of this ratio is usually 5, preferably 3, and more preferably 2.

[0068] The weight-average molecular weight (Mw) of the polymer [B] measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but the lower limit is preferably 1,000, more preferably 2,000, even more preferably 2,500, and particularly preferably 3,000. On the other hand, the upper limit of the Mw of the polymer [B] is preferably 50,000, more preferably 30,000, even more preferably 20,000, and particularly preferably 15,000. By setting the Mw of the polymer [B] within the above range, the coatability and development defect suppression properties of the resist composition are improved. If the Mw of the polymer [B] is less than the above lower limit, a resist film having sufficient heat resistance may not be obtained. Conversely, if the Mw of the polymer [B] exceeds the above upper limit, the developability of the resist film may be reduced.

[0069] The lower limit of the ratio (Mw / Mn) of the Mw of the polymer (B) to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 1. On the other hand, the upper limit of the ratio is preferably 5, more preferably 3, and still more preferably 2.

[0070] In this specification, the Mw and Mn of the polymer are values ​​measured using gel permeation chromatography (GPC).

[0071] The polymer [A] and the polymer [B] may contain a low-molecular-weight component having a molecular weight of 1,000 or less. The upper limit of the content of the low-molecular-weight component in the 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 of this content is, for example, 0.01% by mass. By setting the content of the low-molecular-weight component in the polymer [A] and the polymer [B] within the above range, the lithography performance of the resist composition can be further improved.

[0072] The content of low molecular weight components in the polymer in this specification is a value measured using high performance liquid chromatography (HPLC).

[0073] The lower limit of the fluorine atom content in the polymer (A) and the polymer (B) is preferably 1% by mass, more preferably 2% by mass, even more preferably 4% by mass, and particularly preferably 7% by mass. On the other hand, the upper limit of the fluorine atom content is preferably 60% by mass, more preferably 40% by mass, and even more preferably 30% by mass. Here, the fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer determined by C-NMR spectrum measurement.

[0074] (Method of Synthesizing Polymer [A] and Polymer [B]) The polymer [A] and the polymer [B] can be produced, for example, by polymerizing monomers corresponding to each predetermined structural unit in an appropriate polymerization reaction solvent using a polymerization initiator such as a radical polymerization initiator. Specific synthesis methods include, for example, a method in which a solution containing a monomer and a radical polymerization initiator is dropped into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction, a method in which a solution containing a monomer and a solution containing a radical polymerization initiator are dropped separately into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction, and a method in which multiple solutions containing each monomer and a solution containing a radical polymerization initiator are dropped separately into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction.

[0075] Examples of the radical polymerization initiator include azo radical initiators such as azobisisobutyronitrile (AIBN), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobisisobutyrate; and peroxide radical initiators such as benzoyl peroxide, t-butyl hydroperoxide, and cumene hydroperoxide. Of these, preferred radical polymerization initiators are AIBN and dimethyl 2,2'-azobisisobutyrate, with AIBN being more preferred. These radical initiators can be used alone or in combination of two or more.

[0076] The solvent used in the polymerization can be, for example, the same as the solvent that may be contained in the resist composition, which will be described later.

[0077] The lower limit of the reaction temperature in the polymerization is preferably 40° C., more preferably 50° C. Meanwhile, the upper limit of the reaction temperature is preferably 150° C., more preferably 120° C. The lower limit of the reaction time in the polymerization is preferably 1 hour, while the upper limit of the reaction time is preferably 48 hours, more preferably 24 hours.

[0078] The polymer [A] and the polymer [B] are preferably recovered by a reprecipitation method. That is, after the reaction is completed, the reaction solution is poured into a reprecipitation solvent to recover the target polymer as a powder. As the reprecipitation solvent, alcohols, alkanes, etc. can be used alone or in combination of two or more. In addition to the reprecipitation method, the polymer can also be recovered by removing low-molecular-weight components such as monomers and oligomers by a separation operation, a column operation, an ultrafiltration operation, etc.

[0079] The photosensitizer 2 is a substance other than the substrate that first absorbs light in a photochemical reaction, becomes excited, and transfers the excited energy to the substrate through energy transfer or electron transfer, thereby causing a reaction of the substrate.

[0080] In the resist composition of the present disclosure, compounds represented by the above general formulas (4) to (10) are used as the photosensitizer 2. These photosensitizers can be used alone or in combination of two or more.

[0081] The content of the photosensitizer in the resist composition according to this embodiment is preferably 1 to 40 mass %, more preferably 2 to 30 mass %, and even more preferably 3 to 15 mass %, relative to 100 mass % of the resist composition components excluding the acid generator. When the content of the photosensitizer in the resist composition is within this range, activation of the photoacid generator by the photosensitizer can be enhanced.

[0082] The acid generator 3 is also called a photo acid generator (PAG), and generates an acid upon exposure to light. Here, "generating an acid upon exposure" means that an acid is generated by irradiating the acid generator with radiation (active energy rays) such as light or an electron beam. The acid generated from the acid generator can act on the polymer component described above so as to make the polymer component soluble or insoluble in a developer.

[0083] For example, when the acid generator is irradiated with first radiation having a wavelength of 300 nm or less and is not irradiated with second radiation having a wavelength of more than 300 nm, the light absorption wavelength of the acid generator can change so as to absorb the second radiation.

[0084] Here, the first radiation is an energy ray having a wavelength of 300 nm or less (for example, extreme ultraviolet (EUV) etc.) The wavelength range of the first radiation is not limited as long as it is 300 nm or less, but is preferably 250 nm or less, and more preferably 200 nm or less.

[0085] On the other hand, the second radiation is an energy ray having a wavelength of more than 300 nm (for example, ultraviolet (UV) excluding extreme ultraviolet). The range of the wavelength of the second radiation is not limited as long as it exceeds 300 nm, but is preferably 500 nm or less, and more preferably 400 nm or less.

[0086] In this specification, "irradiating the first radiation but not the second radiation" refers to a state in which only the first radiation is irradiated and the second radiation is not irradiated. Furthermore, "changing the light absorption wavelength so as to absorb the second radiation" refers to a transition or shift of the maximum absorption wavelength for the radiation from the wavelength region of the first radiation to the wavelength region of the second radiation.

[0087] Furthermore, the acid generator decomposes when irradiated with the first radiation and then with the second radiation, but does not decompose when irradiated with the second radiation without irradiating with the first radiation. Here, "irradiation with the second radiation without irradiating with the first radiation" refers to a state in which only the second radiation is irradiated, without irradiating with the first radiation. "irradiation with the first radiation and then with the second radiation" refers to a state in which only the first radiation is irradiated, followed by only the second radiation. "Decomposition of the acid generator" refers to the acid generator changing into two or more different components while generating acid.

[0088] In the resist composition according to this embodiment, the polarity of the acid generator can be increased by the action of an acid. Increasing polarity means that the charge distribution becomes more biased and the hydrophilicity increases. As the polarity of the acid generator increases, the solubility of the acid generator in hydrophilic developers such as organic alkaline solutions increases, while the solubility of the acid generator in hydrophobic developers such as organic solvents decreases.

[0089] In the resist composition according to this embodiment, the acid generator generates an acid when irradiated with the first radiation, and does not generate an acid when irradiated with the second radiation without irradiating with the first radiation.

[0090] That is, the acid generator can generate an acid when irradiated with only the first radiation. Also, the acid generator can generate an acid when irradiated with only the first radiation and then with only the second radiation. Furthermore, the acid generator cannot generate an acid when irradiated with only the second radiation without irradiating with the first radiation.

[0091] That is, before the light absorption wavelength of the acid generator is changed to absorb the second radiation, the acid generator can generate an acid when irradiated with the first radiation, whereas after the light absorption wavelength of the acid generator is changed to absorb the second radiation, the acid generator can generate an acid when irradiated with the second radiation.

[0092] In the resist composition according to this embodiment, the acid generator contains an onium compound that becomes a carbonyl compound when irradiated with the first radiation. That is, the acid generator contains an onium compound, and the onium compound can be converted into a carbonyl compound by being irradiated with only the first radiation. The carbonyl compound may be an onium compound or a compound other than an onium compound.

[0093] In the resist composition according to this embodiment, the onium compound contained in the acid generator is not particularly limited.

[0094] The content of the acid generator in the resist composition according to this embodiment is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 15 parts by mass, per 100 parts by mass of the resist composition components excluding the acid generator.

[0095] In calculating the content of the acid generator, the organic solvent (solvent) is not included in 100 parts by mass of the resist composition components. When the acid generator is contained in the resin as a single unit, that is, when the acid generator is a polymer component, the mass is calculated excluding the polymer main chain.

[0096] In the resist composition according to this embodiment, the acid generator may be used alone or in combination with another acid generator, regardless of whether it is a polymer component or a low-molecular-weight component. Furthermore, in the resist composition, the acid generator may be substituted as part of the polymer component.

[0097] Examples of acid generators other than the above-mentioned acid generators containing onium salts include general-purpose ionic acid generators and non-ionic acid generators. Examples of ionic acid generators include onium salt compounds such as iodonium salts and sulfonium salts other than those mentioned above. Examples of non-ionic acid generators include N-sulfonyloxyimide compounds, oxime sulfonate compounds, organic halogen compounds, and sulfonyldiazomethane compounds.

[0098] When an acid generator other than the above-mentioned acid generator containing an onium salt is contained, the content thereof is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resist composition components excluding the total amount of the acid generator.

[0099] The resist composition of the present disclosure contains a resist base material, a compound represented by any one of the general formulas (4) to (10), and an acid generator (PAG) that generates an acid upon exposure. When the compound represented by any one of the general formulas (4) to (6) absorbs ultraviolet light, it changes to one of the compounds represented by any one of the general formulas (7) to (10), and the absorption wavelength shifts to a longer wavelength, allowing the compound to function as a photosensitizer precursor.

[0100] Furthermore, the compounds represented by the general formulas (4) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change into polar compounds represented by the general formulas (7) to (10). Therefore, by using the general formulas (4) to (6) as photosensitizer precursors, the compounds represented by the general formulas (7) to (10) can be easily removed during simultaneous UV irradiation in a step after EUV exposure, and improvement in dissolution contrast can be expected.

[0101] FIG. 4 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is bonded to an acid generator (PAG)). FIG. 5 is a diagram showing a reaction in which the resist composition of FIG. 4 is activated. In the resist composition of the present disclosure, as shown in FIG. 4, a photosensitizer 2 is preferably bonded to an acid generator (PAG) 3. In the example shown in FIG. 5, a non-polar compound represented by the general formula (6) above is converted into a polar compound represented by the general formula (9) above by absorbing ultraviolet light.

[0102] In the resist composition shown in FIG. 4, the reactivity of each component can be adjusted by the length of the structure in which the photosensitizer 2 and the acid generator (PAG) 3 are bonded to each other.

[0103] In order for the resist composition shown in FIG. 3 to function as a photosensitizer chemically amplified resist, it is preferable that the resist base material, acid generator (PAG), and photosensitizer are present in close proximity to each other in the resist composition.

[0104] Therefore, by binding the photosensitizer to the acid generator (PAG) in this manner, the interaction between the photosensitizer and the acid generator (PAG) in the resist composition becomes stronger, and a resist composition containing such a photosensitizer and acid generator can exhibit high functionality as a photosensitizer-based chemically amplified resist.

[0105] Fig. 6 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer binds to a resist base material). Figs. 7 to 9 are diagrams showing an example of the resist composition of Fig. 6. Fig. 10 is a diagram showing the activation reaction of the resist composition of Fig. 7, Fig. 11 is a diagram showing the activation reaction of the resist composition of Fig. 8, and Fig. 12 is a diagram showing a specific example of the resist composition of Fig. 8.

[0106] In the resist composition of the present disclosure, a photosensitizer 2 is preferably bonded to a resist base material 1, as shown in Fig. 6. The examples shown in Figs. 7 to 9 show three examples in which the compound represented by general formula (6) is bonded to the resist base material (or resist polymer) 1 in different ways.

[0107] In the resist composition shown in FIG. 6, the reactivity of each component can be adjusted by changing the length of the bond between the resist base material 1 and the photosensitizer 2 .

[0108] In the example shown in FIG. 10 , the compound represented by the general formula (6) attached to the resist substrate 1 is detached from the resist substrate 1 by absorbing ultraviolet light, thereby generating a polar compound represented by the general formula (9).

[0109] In the example shown in Fig. 11, the compound represented by the general formula (6) bonded to the resist base material 1 is converted into the polar compound represented by the general formula (9) by absorbing ultraviolet light while remaining bonded to the resist base material 1. Specific examples of the example shown in Fig. 11 include the compounds shown in Fig. 12. In Fig. 12, MOR stands for metal oxide resist.

[0110] Because the photosensitizer is bound to the resist base material 1 in this manner, when the acid generator (PAG) is present in the resist composition near the resist base material 1, the interaction between the resist base material 1, the acid generator (PAG), and the photosensitizer is enhanced. As a result, a resist composition containing such a photosensitizer and resist base material can exhibit high functionality as a photosensitizer-based chemically amplified resist.

[0111] 13 is a diagram showing the composition of a resist composition (a composition in which an acid generator (PAG) is bound to a resist base material, and a photosensitizer is bound to the acid generator (PAG)). As shown in FIG. 13, the resist composition of the present disclosure preferably has an acid generator (PAG) 3 bound to a resist base material 1, and further has a photosensitizer 2 bound to the acid generator (PAG) 3.

[0112] In the resist composition shown in FIG. 13, the reactivity of each component can be adjusted by the length of the bond between the resist base material 1 and the acid generator (PAG) 3 and / or the bond between the photosensitizer 2 and the acid generator (PAG) 3.

[0113] In this manner, the acid generator (PAG) 3 is bound to the resist base material 1, and the photosensitizer 2 is bound to the acid generator (PAG) 3 in the resist composition, thereby enhancing the interaction between the photosensitizer 2 and the acid generator (PAG) 3 in the resist composition. Furthermore, the acid generator (PAG) 3 is bound to the resist base material 1, thereby enhancing the interaction between the photosensitizer, the acid generator (PAG) 3, and the resist base material 1 in the resist composition. Therefore, a resist composition in which such an acid generator is bound to the resist base material and the photosensitizer is bound to the acid generator (PAG) can exhibit even greater functionality as a photosensitizer-based chemically amplified resist.

[0114] The resist composition of the present disclosure may contain a resist base material, at least one compound represented by any one of the general formulas (4) to (10), an acid generator (PAG), and a quencher (PDB). The compounds represented by any one of the general formulas (4) to (10) are examples of photosensitizers used in resist compositions containing the quencher of the present disclosure.

[0115] A quencher, also known as a photodegradable base (PDB), has basicity against acids. A quencher is a component that acts on an acid (e.g., neutralizes) and suppresses the acid generated from an acid generator. The term "basic" refers to the ability to act as a base relative to an acid. Therefore, quenchers that have basicity are not limited to those that have alkaline properties, but also include weak acid salts that can become bases against acids.

[0116] The quencher loses its basicity to acids when irradiated with the first radiation (radiation having a wavelength of 300 nm or less), for example, and retains its basicity to acids when irradiated with the second radiation (radiation having a wavelength of more than 300 nm) without irradiating with the first radiation.

[0117] That is, the quencher loses its basicity to acids when irradiated with only the first radiation. Furthermore, the quencher also loses its basicity to acids when irradiated with only the second radiation after being irradiated with only the first radiation. Furthermore, the quencher maintains (does not lose) its basicity to acids when irradiated with only the second radiation without being irradiated with the first radiation.

[0118] That is, before the light absorption wavelength of the quencher changes to absorb the second radiation, the quencher loses its basicity to acids when irradiated with the first radiation, whereas after the light absorption wavelength of the quencher changes to absorb the second radiation, the quencher loses its basicity to acids when irradiated with the second radiation.

[0119] The quencher is not particularly limited and includes, for example, an onium compound that becomes a carbonyl compound when irradiated with the first radiation. That is, examples include an onium compound that is converted into a carbonyl compound when irradiated with radiation. The carbonyl compound may be an onium compound or a compound other than an onium compound.

[0120] The method for synthesizing the onium salt is not particularly limited, but for example, the method for synthesizing onium salts (sulfonium salts and iodonium salts) disclosed in International Publication WO 2018 / 074382 can be applied.

[0121] The content of the quencher in the resist composition according to this embodiment is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 3 to 15 parts by mass, per 100 parts by mass of the resist composition components excluding the quencher.

[0122] In calculating the content of the quencher, the organic solvent (solvent) is not included in 100 parts by mass of the resist composition components. When the quencher is contained in the resin as a single unit, that is, when the quencher is a polymer component, the mass is calculated excluding the polymer main chain.

[0123] In the resist composition according to this embodiment, the quencher may be used alone or in combination with another quencher, regardless of whether it is a polymer component or a low-molecular-weight component. Furthermore, in the resist composition, the quencher may be substituted as part of the polymer component.

[0124] Quenchers other than the above-mentioned onium salt-containing quenchers include general-purpose ionic quenchers and nonionic quenchers. Examples of ionic quenchers include onium salt compounds such as iodonium salts and sulfonium salts other than those mentioned above. Examples of nonionic quenchers include N-sulfonyloxyimide compounds, oxime sulfonate compounds, organic halogen compounds, and sulfonyldiazomethane compounds.

[0125] When a quencher other than the above-mentioned onium salt-containing quencher is contained, the content thereof is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resist composition components excluding the total amount of quenchers.

[0126] In addition to the polymer component, acid generator, and quencher described above, the resist composition according to this embodiment typically contains a solvent (such as an organic solvent), and may further contain a radiation-sensitive sensitizer, a radical scavenger, a crosslinking agent, a surfactant, a stabilizer, a dye, and other additives.

[0127] The resist composition of the present disclosure contains a resist base material, a compound represented by any of the general formulas (4) to (10), an acid generator (PAG) that generates an acid upon exposure, and a quencher that is basic to acids. When the compound represented by any of the general formulas (4) to (6) absorbs ultraviolet light, it changes to a compound represented by any of the general formulas (7) to (10), and the absorption wavelength shifts to a longer wavelength, so that the compound can function as a photosensitizer precursor.

[0128] Furthermore, the compounds represented by the general formulas (4) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change into polar compounds represented by the general formulas (7) to (10). Therefore, by using the general formulas (4) to (6) as photosensitizer precursors, the compounds represented by the general formulas (7) to (10) can be easily removed during simultaneous UV irradiation in a step after EUV exposure, and improvement in dissolution contrast can be expected.

[0129] 14 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is bonded to a quencher (PDB)). As shown in FIG. 14, the resist composition of the present disclosure preferably has a photosensitizer 2 bonded to a quencher (PDB) 4.

[0130] In order for a resist composition containing a quencher (PDB) to function as a photosensitizer chemically amplified resist, it is preferable that the photosensitizer and quencher (PDB) are present in close proximity to each other in the resist composition.

[0131] In the resist composition shown in FIG. 14, the reactivity of each component can be adjusted by adjusting the length of the structure in which the photosensitizer 2 and the quencher (PDB) 4 are bonded to each other.

[0132] Therefore, by binding the photosensitizer to the quencher (PDB) in this manner, the interaction between the photosensitizer and the quencher (PDB) in the resist composition is enhanced, and a resist composition containing such a photosensitizer and quencher (PDB) can exhibit high functionality as a photosensitizer-based chemically amplified resist.

[0133] 15 and 16 are diagrams showing the composition of the resist composition (the composition in which the photosensitizer ionically bonds to the resist base material).

[0134] In the resist composition of the present disclosure, the photosensitizer 2 (a compound represented by any one of the above general formulas (4) to (10)) may be ionically bonded to the resist base material. The form of the ionic bond is not particularly limited. For example, in the example shown in FIG. 15 , the resist base material is an anion, the photosensitizer is a cation, and the two are bonded together by Coulomb force. In the example shown in FIG. 16 , the resist base material is a cation, and the photosensitizer is an anion, and the two are bonded together by Coulomb force.

[0135] Because the photosensitizer is ionically bonded to the resist base in this way, the resist base and photosensitizer can be easily removed when UV light is irradiated all at once in the process after EUV exposure, which is expected to improve dissolution contrast.

[0136] 17A to 17C are diagrams showing a conventional process for a photosensitizer chemically amplified resist, and 18A to 18C are diagrams showing a process for a photosensitizer chemically amplified resist using the resist composition of the present disclosure.

[0137] 17A to 17C are disclosed to facilitate comparison with FIGS. 18A to 18C, and the arrangement of the components in FIGS. 17A to 17C has no particular meaning.

[0138] In a conventional photosensitizer chemically amplified resist process, when a resist composition containing a resist base material 1, a photosensitizer precursor (PP) 2, an acid generator (PAG) 3, and a quencher (QC) 4 is exposed to EUV on a substrate B, the photosensitizer precursor (PP) 2 is transformed into an activated photosensitizer (PS) 2' (FIG. 17A). Next, when the resist composition is developed in a developer E (FIG. 17B), only the exposed portions of the resist composition are removed (FIG. 17C).

[0139] However, in conventional photosensitizer chemically amplified resist processes, the photosensitizer (PS) 2′ after activation of the photosensitizer precursor (PP) 2 is non-polar, and therefore cannot be completely removed by development, resulting in a decrease in dissolution contrast.

[0140] In contrast, in the process for producing a photosensitizer-based chemically amplified resist using the resist composition of the present disclosure, the compounds represented by the above general formulas (4) to (10) are used as photosensitizers. When the resist composition is exposed to EUV, the photosensitizer precursor (PP)2 is activated to produce the photosensitizer (PS)2', which is polar and therefore removed by development, thereby improving the dissolution contrast (Figures 18A to 18C).

[0141] 19 to 21 are diagrams showing embodiments of a method for producing a resist composition according to the present disclosure. In the method for producing a resist composition according to the present disclosure, at least one compound represented by any one of the general formulas (4) to (10) above is mixed into a resist base material.

[0142] For example, a compound represented by any one of the general formulas (4) to (10) above as a photosensitizer is mixed with a resist solution in a container A to prepare a mixed solution 6 (FIG. 19). This causes ion exchange between the compound represented by any one of the general formulas (4) to (10) above and the resist solution (resist base), yielding a resist composition (mixed solution 6) in which the resist base (cation) and the photosensitizer (anion) are ionically bonded, as shown in FIG.

[0143] Furthermore, the method for producing the resist composition (e.g., ion exchange between the resist base and the photosensitizer) may be performed after the formation of the resist base material. For example, a solution of a compound represented by any one of the general formulas (4) to (10) as a photosensitizer (photosensitizer 2) may be dropped from the discharge port C onto the resist base material (film) formed on the substrate B, thereby forming a film 6' in which the photosensitizer is infiltrated into the resist base material.

[0144] In the resist composition production method of the present disclosure, the resist composition can be obtained by mixing at least one compound represented by general formulas (4) to (10) with a resist base material, which makes it easy to produce the resist composition.

[0145] Furthermore, in the resist composition manufacturing method of the present disclosure, by performing ion exchange between the resist base material and at least one compound represented by general formulas (4) to (10), the resist composition obtained has an ionic bond between the resist base material (cation) and the photosensitizer (anion). Therefore, a resist composition can be obtained from which the photosensitizer can be easily removed when performing collective UV irradiation in a step after EUV exposure.

[0146] 22 to 25 are diagrams showing examples of a substrate processing apparatus using the resist composition of the present disclosure. As shown in Fig. 22, a substrate processing apparatus 10 of the present disclosure includes a darkroom 11, an exposure unit 12, a development unit 13, and an opening / closing window 14.

[0147] In the substrate processing apparatus 10, a substrate B on which a resist film is to be formed is placed in a darkroom 11. An exposure unit 12 exposes the resist composition (a resist composition containing a compound represented by any one of the general formulas (4) to (10) above as a sensitizer) formed as a film on the substrate B. A development unit 13 develops the exposed resist composition.

[0148] The opening / closing window 14 is closed during exposure and development, and is opened when the substrate B is loaded or unloaded before or after processing. The opening / closing window 14 may be provided arbitrarily, and the substrate processing apparatus 10 may have a structure provided with the opening / closing window.

[0149] The process in the substrate processing apparatus 10 is not particularly limited, and for example, a two-stage exposure lithography process is performed. Such a lithography process, such as a resist pattern formation method, includes a film formation step of forming a resist film on a substrate using the resist composition, a pattern exposure step of irradiating the resist film with a first radiation (e.g., radiation having a wavelength of 300 nm or less) through a mask, a flood exposure step of irradiating the resist film after the pattern exposure step with a second radiation (e.g., radiation having a wavelength of more than 300 nm), a baking step (PEB) of heating the resist film after the flood exposure step, and a step of contacting the resist film after the baking step with a developer.

[0150] In addition, the above process may include a post-exposure bake (PEB) step between the patternwise exposure step and the floodwise exposure step, in which the resist film after the patternwise exposure step is heated. Furthermore, instead of including the post-exposure bake (PEB) step, the bake step (PEB) in which the resist film after the floodwise exposure step is heated may be omitted.

[0151] In the floodwise exposure step, the wavelength of the second radiation (radiation having a wavelength of more than 300 nm) to be irradiated is preferably 350 nm or more, more preferably 390 nm or more. The upper limit of the wavelength of the second radiation is not particularly limited, but is preferably 500 nm or less, more preferably 450 nm or less, in that the peak absorption wavelengths of the compounds represented by the general formulae (7) to (10) after activation of the compounds represented by the general formulae (4) to (10) are in the range of 350 nm to 400 nm.

[0152] Such a process in the substrate processing apparatus 10 is an example of a substrate processing method of the present disclosure.

[0153] The substrate processing apparatus of the present disclosure uses a resist composition containing a compound represented by any one of the general formulas (4) to (10) as a sensitizer. Upon absorbing ultraviolet light, the compounds represented by the general formulas (4) to (6) are converted to compounds represented by the general formulas (7) to (10), resulting in a longer absorption wavelength. Therefore, the compounds represented by the general formulas (4) to (10) may be unexpectedly activated when exposed to visible light close to ultraviolet light (short-wavelength visible light). Therefore, in the substrate processing apparatus of the present disclosure, exposure and development by ultraviolet irradiation are performed in a darkroom, thereby preventing such unexpected activation.

[0154] Furthermore, in the substrate processing method of the present disclosure, a resist composition containing a compound represented by any one of the general formulas (4) to (10) is used. As described above, the compounds represented by any one of the general formulas (4) to (6) (compounds having a xanthylium structure, an acridinium structure, or an anthracene structure) change into the compounds represented by any one of the general formulas (7) to (10), respectively, upon absorbing ultraviolet light, and the absorption wavelength shifts to a longer wavelength. Therefore, by using the compounds represented by any one of the general formulas (4) to (6), etc. as a photosensitizer precursor, the photosensitizer that has changed into the compound represented by any one of the general formulas (7) to (10) can be treated with ultraviolet light close to visible light when irradiated with UV light all at once in the process after EUV exposure.

[0155] Furthermore, as described above, the compounds represented by the general formulas (4) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they are converted into the polar compounds represented by the general formulas (7) to (10), respectively. Therefore, when UV light is irradiated all at once in the process after EUV exposure, the compounds represented by the general formulas (7) to (10) can be easily removed, and an improvement in dissolution contrast can be expected.

[0156] 23 , the substrate processing apparatus 20 according to the present disclosure has an infrared monitor. The form of the infrared monitor is not particularly limited, but may be configured, for example, by an infrared lamp 24 and an infrared camera 25. The infrared monitor (the infrared lamp 24 and the infrared camera 25) is provided in the darkroom 21 and can monitor the inside of the darkroom 21.

[0157] As described above, the compounds represented by the general formulas (4) to (10) contained in the resist composition as sensitizers may be unexpectedly activated when exposed to visible light close to ultraviolet light (short-wavelength visible light). Therefore, in the substrate processing apparatus 20 of the present disclosure, an infrared monitor is provided in the darkroom to prevent exposure to short-wavelength visible light and to monitor substrate processing even in such a darkroom.

[0158] 24, a substrate processing apparatus 30 according to the present disclosure includes a coating unit 31, a flow path 32, and a nozzle 33. The coating unit 31 is a spin coater, and a substrate B to be coated with a resist composition is fixed to the coating unit 31.

[0159] A resist composition flows through the flow path 32. The flow path 32 is composed of a flow path 32A and a branching flow path 32B. A resist solution flows through the flow path 32A, and a latent photosensitizer (photosensitizer precursor) solution flows through the flow path 32B. In the flow path 32, the resist solution flowing through the flow path 32A is mixed with the latent photosensitizer (photosensitizer precursor) solution flowing through the flow path 32B. Note that the configuration of the flow path 32 is not limited thereto, and it may be such that the latent photosensitizer (photosensitizer precursor) solution flows through the flow path 32A, and the resist solution flows through the flow path 32B.

[0160] The nozzle 33 is disposed above the coating unit 31 and communicates with the tip of the flow path 32. In the substrate processing apparatus 30 of the present disclosure, the resist composition mixed in the flow path 32 is discharged from the nozzle 33 and coated onto the substrate B. This makes it possible to carry out the above-described method for producing a resist composition (mixing at least one compound represented by the above general formulas (4) to (10) into a resist base material).

[0161] 25 , a substrate processing apparatus 40 according to the present disclosure has a flow path 42 and a nozzle 43. The flow path 42 is composed of a flow path 42A and a branching flow path 42B. The flow path 42A communicates with the nozzle 43, and a resist composition (resist solution and latent photosensitizer solution) flows through the flow path 42A. The flow path 42A is an example of a first flow path in the substrate processing apparatus according to the present disclosure.

[0162] The flow path 42B is connected to the flow path 42A, and an alkaline solution flows through the flow path 42B. The flow path 42B is an example of a second flow path in the substrate processing apparatus of the present disclosure. The alkaline solution is flowed into the flow path 42 before the resist composition flows in order to replace (neutralize) the acid remaining in the flow path 42. After the alkaline solution has flowed, it is preferable to wash the flow path 42 with deionized water (DIW).

[0163] The nozzle 43 is connected to the tip of the flow path 42A and discharges the resist composition. The nozzle 43 is an example of a nozzle in the substrate processing apparatus of the present disclosure.

[0164] In the substrate processing apparatus 40 of the present disclosure, the resist composition flowing in the flow path 42 contains a latent photosensitizer solution that is sensitive to acid, and therefore, if acid is present in the flow path 42, the resist composition may be deteriorated by the acid. Therefore, in the substrate processing apparatus 40 of the present disclosure, a second flow path (flow path 42B) is provided that communicates with the second flow path (flow path 42A) and through which an alkaline solution flows. This allows the inside of the flow path 42 to be replaced with an alkaline solution before the resist composition is flowed, thereby preventing deterioration of the resist composition by acid.

[0165] The above-disclosed embodiments include, for example, the following aspects.

[0166] (Appendix 1) A resist composition containing at least one compound represented by the following general formulas (11), (12) and (13). [In general formula (11), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y １ are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (12), R ５ ~R９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (13), R １０ ~R １５ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom; ３ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0167] (Appendix 2) A resist composition containing a compound represented by the following general formula (14): [In general formula (14), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y １are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0168] (Appendix 3) A resist composition containing a compound represented by the following general formula (15): [In general formula (15), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0169] (Appendix 4) A resist composition containing a compound represented by the following general formula (16): [In general formula (16), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

[0170] (Appendix 5) A resist composition containing a compound represented by the following general formula (17): [In general formula (17), R １ ~R ３are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ is an oxygen atom or a sulfur atom.

[0171] (Appendix 6) A resist composition containing a compound represented by the following general formula (18): [In general formula (18), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom.

[0172] (Appendix 7) A resist composition containing a compound represented by the following general formula (19): [In general formula (19), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched, or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms.

[0173] (Appendix 8) A resist composition containing a compound represented by the following general formula (20): [In general formula (20), R １０ ~R １４are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom.

[0174] (Appendix 9) The resist composition according to any one of Appendices 1 to 8, comprising: a resist base material; at least one compound represented by any one of general formulas (11) to (20); and an acid generator that generates an acid upon exposure.

[0175] (Appendix 10) The resist composition according to Appendix 9, wherein the compound is bonded to the acid generator.

[0176] (Appendix 11) The resist composition according to appendix 9 or 10, wherein the compound is bonded to the resist base material.

[0177] (Appendix 12) The resist composition according to any one of Appendices 9 to 11, wherein the acid generator is bonded to the resist base material, and the compound is bonded to the acid generator.

[0178] (Appendix 13) The resist composition according to any one of Appendices 1 to 12, comprising: a resist base material; at least one compound represented by any one of general formulas (11) to (20); an acid generator that generates an acid upon exposure; and a quencher that is basic to an acid.

[0179] (Appendix 14) The resist composition according to Appendix 13, wherein the compound is bound to the quencher.

[0180] (Appendix 15) The resist composition according to any one of Appendices 9 to 14, wherein the compound is ionically bonded to the resist base material.

[0181] (Appendix 16) A method for producing a resist composition according to any one of Appendices 1 to 15, comprising mixing at least one compound represented by any one of general formulas (11) to (20) with a resist base material.

[0182] (Appendix 17) The method for producing a resist composition according to Appendix 16, further comprising ion-exchanging the resist base material with the compound.

[0183] (Supplementary Note 18) A substrate processing apparatus comprising: a darkroom in which a substrate is placed; an exposure unit provided in the darkroom, which exposes a resist composition according to any one of Supplementary Notes 1 to 15 that has been formed into a film on the substrate; and a development unit provided in the darkroom, which develops the exposed resist composition.

[0184] (Supplementary Note 19) The substrate processing apparatus according to Supplementary Note 18, comprising: a nozzle for ejecting the resist composition; a first flow path communicating with the nozzle and through which the resist composition flows; and a second flow path communicating with the first flow path and through which an alkaline solution flows.

[0185] (Supplementary Note 20) A substrate processing method, comprising: a film formation step of forming a resist film on a substrate, the resist film comprising the resist composition according to any one of Supplementary Notes 1 to 15; a pattern exposure step of irradiating the resist film with radiation having a wavelength of 300 nm or less via a mask; a flood exposure step of irradiating the resist film after the pattern exposure step with radiation having a wavelength of more than 300 nm; a bake step of heating the resist film after the flood exposure step; and a step of contacting the resist film after the bake step with a developer.

[0186] Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to these embodiments, and various modifications and changes are possible within the scope of the disclosure described in the claims.

[0187] 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.

[0188] REFERENCE SIGNS LIST 1 resist base material 2 photosensitizer (photosensitizer precursor) 2' photosensitizer (activated photosensitizer) 3 acid generator (PAG) 4 quencher (PDB) B substrate E developing device A container C discharge port 6 mixed solution 6' film 10, 20, 30, 40 substrate processing device 11, 21 darkroom 12, 22 exposure section 13, 23 developing section 14 opening / closing window 24 infrared lamp 25 infrared camera 31, 41 coating section 32, 32A, 32B, 42, 42A, 42B flow path 33, 43 nozzle

Claims

1. A resist composition containing at least one compound represented by the following general formulas (1), (2) and (3): [In general formula (1), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y １ are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (2), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [In general formula (3), R １０ ~R １５ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom; ３ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

2. A resist composition containing a compound represented by the following general formula (4): [In general formula (4), R １ ~R ４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ , Y １ are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

3. A resist composition containing a compound represented by the following general formula (5): [In general formula (5), R ５ ~R ９ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

4. A resist composition containing a compound represented by the following general formula (6): [In general formula (6), R ５ ~R ９ each independently represents one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom.

5. A resist composition containing a compound represented by the following general formula (7): [In general formula (7), R １ ~R ３ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; １ is an oxygen atom or a sulfur atom.

6. A resist composition containing a compound represented by the following general formula (8): [In general formula (8), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ２ is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom.

7. A resist composition containing a compound represented by the following general formula (9): [In general formula (9), R ５ ~R ８ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms.

8. A resist composition containing a compound represented by the following general formula (10): [In general formula (10), R １０ ~R １４ are each independently any one selected from the group consisting of an optionally substituted linear, branched or cyclic alkyl group having 1 to 12 carbon atoms; an optionally substituted linear, branched or cyclic alkenyl group having 1 to 12 carbon atoms; an optionally substituted aryl group having 6 to 14 carbon atoms; and an optionally substituted heteroaryl group having 4 to 12 carbon atoms; ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom.

9. The resist composition according to any one of claims 1 to 8, comprising: a resist base material; at least one compound represented by any one of general formulas (1) to (10); and an acid generator that generates an acid upon exposure.

10. The resist composition according to claim 9, wherein the compound is bound to the acid generator.

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

12. The resist composition according to claim 9, wherein the acid generator is bound to the resist base material, and the compound is bound to the acid generator.

13. The resist composition according to any one of claims 1 to 8, comprising: a resist base material; at least one compound represented by any one of general formulas (1) to (10); an acid generator that generates an acid upon exposure; and a quencher that is basic to an acid.

14. The resist composition of claim 13, wherein the compound is bound to the quencher.

15. The resist composition according to claim 9, wherein said compound is ionically bonded to said resist base material.

16. A method for producing the resist composition according to any one of claims 1 to 8, comprising mixing at least one compound represented by any one of general formulas (1) to (10) with a resist base material.

17. The method for producing a resist composition according to claim 16, further comprising the step of carrying out ion exchange between the resist base material and the compound.

18. A substrate processing apparatus comprising: a darkroom for placing a substrate; an exposure section provided within the darkroom for exposing a resist composition according to any one of claims 1 to 8 that has been formed into a film on the substrate; and a development section provided within the darkroom for developing the exposed resist composition.

19. The substrate processing apparatus according to claim 18, comprising: a nozzle for ejecting the resist composition; a first flow path communicating with the nozzle and through which the resist composition flows; and a second flow path communicating with the first flow path and through which an alkaline solution flows.

20. A substrate processing method comprising: a film formation step of forming a resist film containing the resist composition according to any one of claims 1 to 8 on a substrate; a pattern exposure step of irradiating the resist film with radiation having a wavelength of 300 nm or less through a mask; a flood exposure step of irradiating the resist film after the pattern exposure step with radiation having a wavelength of more than 300 nm; a bake step of heating the resist film after the flood exposure step; and a step of contacting the resist film after the bake step with a developer.

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