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

Abstract

To provide a resist composition capable of improving dissolution contrast.SOLUTION: A resist composition contains at least one compound represented by general formula (1) below, or specific general formula (2) or (3).SELECTED DRAWING: None

Description

[Technical field]

[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. [Background technology]

[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 the EUV light, and further acid is generated from the photoacid generator through energy transfer, etc.

[0003] Patent Document 1 discloses a technique of using a compound that changes from an acetal structure to a ketone structure in response to an external stimulus (light, acid, etc.) as a photosensitizer precursor used in a PSCAR process for EUV exposure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP2018-188458A Summary of the Invention [Problem to be solved by the invention]

[0005] In conventional technology, when the acetal structure changes to a ketone structure, the conjugated range is connected and the absorption wavelength becomes longer, but since there is no change in polarity, 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. [Means for solving the problem]

[0007] A resist composition according to one embodiment of the present disclosure contains at least one compound represented by the following general formulas (1) to (3). [ka] [In the general formula (1), R1 to R4 each independently represent 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; X1 and Y1 each independently represent one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [ka] [In the general formula (2), R5 to R9 each independently represent 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; X2 is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y2 is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [ka] [In general formula (3), R 10 ~R 15each 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; X3 is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom; Y3 is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Effect of the Invention

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

[0009] [Figure 1] 3 is a graph showing the absorption wavelength before activation of a photosensitizer (photosensitizer precursor) used in a resist composition. [Diagram 2] 2 is a graph showing the absorption wavelength after activation of the photosensitizer in FIG. 1. [Diagram 3] FIG. 2 is a diagram showing the composition of a resist composition. [Figure 4] FIG. 2 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is bonded to an acid generator (PAG)). [Diagram 5] FIG. 5 is a diagram showing the activation reaction of the resist composition of FIG. [Figure 6] FIG. 2 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is bonded to a resist base material). [Figure 7] FIG. 7 is a diagram showing an example of the resist composition of FIG. [Figure 8] FIG. 7 is a diagram showing an example of the resist composition of FIG. [Figure 9] FIG. 7 is a diagram showing an example of the resist composition of FIG. [Figure 10] FIG. 8 is a diagram showing the activation reaction of the resist composition of FIG. 7. [Figure 11] FIG. 9 is a diagram showing the activation reaction of the resist composition of FIG. 8. [Figure 12] FIG. 9 is a diagram showing a specific example of the resist composition of FIG. [Figure 13] FIG. 2 shows the composition of a resist composition (a composition in which a photoacid generator (PAG) is bonded to a resist base material, and a photosensitizer is bonded to the photoacid generator (PAG)). [Figure 14] FIG. 2 shows the composition of a resist composition (composition in which a photosensitizer binds to a quencher (PDB)). [Figure 15] FIG. 2 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is ionically bonded to a resist base material). [Figure 16] FIG. 2 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer is ionically bonded to a resist base material). [Figure 17] 1 is a diagram showing a conventional photosensitizer chemically amplified resist process. [Figure 18] FIG. 2 is a diagram showing a photosensitizer chemically amplified resist process using the resist composition of the present disclosure. [Figure 19] 1A to 1C are diagrams illustrating an embodiment of producing a resist composition of the present disclosure. [Figure 20] 1A to 1C are diagrams illustrating an embodiment of producing a resist composition of the present disclosure. [Figure 21] 1A to 1C are diagrams illustrating an embodiment of producing a resist composition of the present disclosure. [Figure 22] FIG. 1 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure. [Diagram 23] FIG. 1 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure. [Figure 24] FIG. 1 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure. [Diagram 25] FIG. 1 is a diagram showing a substrate processing apparatus using a resist composition of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In addition, common parts in the drawings may be denoted by the same or corresponding reference numerals, and the description 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) to (6). These compounds can function as a photosensitizer (a precursor of a photosensitizer) in the resist composition. [ka] [ka] [ka]

[0012] The compound represented by the general formula (1) contains a heterocyclic ring having three condensed six-membered rings, C 13 H 10 It has a skeleton of X1 (wherein X1 is an element of Group 16 of the periodic table excluding Po) (hereinafter, may be referred to as a xanthylium skeleton or a xanthylium structure).

[0013] In general formula (1), R1 to R4 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; and X1 and Y1 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 optionally substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms 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 adamantane-1-yl group, an adamantane-2-yl group, a norbornane-1-yl group and a norbornane-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 replaced 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 condensed polycyclic aromatic hydrocarbon groups in which at least two of the monocyclic aromatic hydrocarbons are condensed.

[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] Of these, the compound represented by formula (1) is preferably one in which X1 is an oxygen atom or a sulfur atom, and more preferably one in which X1 is an oxygen atom.

[0019] The compound represented by the general formula (2) contains a heterocyclic ring having three condensed six-membered rings, C 13 H 10 It has a skeleton of X2 (wherein X2 is an element of Group 15 of the periodic table excluding Bi) (hereinafter, may be referred to as an acridinium skeleton or an acridinium structure).

[0020] In general formula (2), R5 to 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; X2 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, and Y2 is 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 optionally substituted straight-chain, branched-chain or cyclic alkyl group having 1 to 12 carbon atoms 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 adamantane-1-yl group, an adamantane-2-yl group, a norbornane-1-yl group and a norbornane-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 replaced 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 condensed polycyclic aromatic hydrocarbon groups in which at least two of the monocyclic aromatic hydrocarbons are condensed.

[0024] Examples of the heteroaryl group having 4 to 12 carbon atoms which may have a substituent include those which contain 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] Of these, the compound represented by formula (2) is preferably one in which X2 is a nitrogen atom or a phosphorus atom, and more preferably one in which X2 is a nitrogen atom.

[0026] The compound represented by the general formula (3) is a heterocyclic compound having three fused six-membered rings, C 13 H 10 It has a skeleton of X3 (wherein X3 is an element of Group 14 of the periodic table excluding Pb) (hereinafter, may be referred to as an anthracene skeleton or an anthracene structure).

[0027] In addition, in the 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; X3 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, and Y3 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 adamantane-1-yl group, an adamantane-2-yl group, a norbornane-1-yl group and a norbornane-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 replaced 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 condensed polycyclic aromatic hydrocarbon groups in which at least two of the monocyclic aromatic hydrocarbons are condensed.

[0031] Examples of the heteroaryl group having 4 to 12 carbon atoms which may have a substituent include those which contain 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] Of these, the compound represented by formula (3) is preferably one in which X3 is a carbon atom or a silicon atom, and more preferably one in which X3 is 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 absorbing ultraviolet light and activating the compound represented by general formula (1). [ka]

[0034] In general formula (7), R1 to R4 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; and X1 is an oxygen atom or a sulfur atom.

[0035] The compound represented by general formula (7) has in common with the compound represented by general formula (1) above in that it has a xanthylium skeleton, but differs in that it is a polar cation in which R4-Y1- has been removed from the 10-position of the xanthylium skeleton.

[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). [ka] In general formula (8), R5 to 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; and X2 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 general formula (8) is similar to the compound represented by general formula (2) in that it has an acridinium skeleton, but differs from it in that it is a polar cation in which R6 has been removed from the 5-position (X2) of the acridinium skeleton and R9-Y2- has been removed from the 10-position of the acridinium skeleton.

[0038] The compound represented by the general formula (8) is preferably one in which X2 is a nitrogen atom, that is, a compound represented by the following general formula (9). [ka]

[0039] In general formula (9), R5 to 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.

[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. [ka]

[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; and X3 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 (X3) of the anthracene skeleton is R 11 is eliminated, and R is released from the 10th position of the anthracene skeleton. 15 The compound represented by the general formula (10) is a weak cationic compound 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 the 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 Fig. 1, the photosensitizer precursor before absorbing UV light (before activation) has an absorption wavelength peak at about 250 nm to 300 nm. In contrast, in Fig. 2, the photosensitizer precursor after absorbing UV light (after activation) has an absorption wavelength peak at about 350 nm to 400 nm.

[0045] That is, it is expected that the compounds represented by the above general formulas (1) to (6) (compounds having a xanthylium structure, an acridinium structure, or anthracene structure) and the like will change to the compounds represented by the above general formulas (7) to (10) by absorbing ultraviolet light, and the absorption wavelength will become longer. For this reason, by using the compounds represented by the above general formulas (1) to (6) and the like as photosensitizer precursors, the photosensitizers that have changed to the compounds represented by the above general formulas (7) to (10) can be treated with ultraviolet light close to visible light when irradiating with UV all at once in the process after EUV exposure.

[0046] Furthermore, the compounds represented by the above general formulas (1) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change to the polar compounds represented by the above general formulas (7) to (10), respectively. Therefore, when UV light is irradiated all at once in the process after EUV exposure, it becomes easy to remove the compounds represented by the above general formulas (7) to (10), 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, and includes 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 may be, for example, 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 by the action of an acid (hereinafter also referred to as "acid dissociable group"). In addition, as a polymer component other than the polymer component, a second polymer (hereinafter also referred to as "polymer [B]") not containing the structural unit (I) may be further included.

[0050] The polymer [A] or the polymer [B] may further have 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 have other structural units other than the structural units (I) to (IV).

[0051] The polymer [A] may further have the structural units (II) to (IV) and 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 the 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 the total structural units constituting the polymer [A] is preferably 10 mol%, more preferably 20 mol%, even more preferably 25 mol%, and particularly preferably 30 mol%. On the other hand, the upper limit of the content is preferably 80 mol%, more preferably 70 mol%, even more preferably 65 mol%, and particularly preferably 60 mol%. By setting the content within the above range, the dissolution contrast of the pattern-exposed and non-exposed parts of the resist composition film formed from the resist composition in the developer can be sufficiently ensured, and as a result, the resolution and the like are improved.

[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, the sensitivity can be further improved when EUV or the like is used as the 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, the sensitivity can be further improved when EUV or the like is used as the 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 light), electron beam, or the like in the patternwise exposure step described later.

[0056] When the polymer [A] has the structural unit (III), the lower limit of the content of the structural unit (III) relative to the total structural units constituting the polymer [A] 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.

[0057] When the polymer component contains the [B] polymer and the [B] polymer has the structural unit (III), the lower limit of the content of the structural unit (III) relative to the total structural units constituting the [B] polymer 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 the -OH group in the 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] The polymer [A] and the polymer [B] further have the structural unit (IV), so that the solubility in the developer can be adjusted to a more appropriate level, and as a result, the lithography performance of the resist composition can be further improved. The adhesiveness between the resist composition film formed from the resist composition and the substrate can be improved. Here, the lactone structure refers to a structure having one ring (lactone ring) containing a group represented by -OC(O)-. The cyclic carbonate structure refers to a structure having one ring (cyclic carbonate ring) containing a group represented by -OC(O)-O-. The sultone structure refers to a structure having one ring (sultone ring) containing a group represented by -OS(O)2-.

[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 a structural unit derived from norbornane lactone-yl (meth)acrylate, a structural unit derived from oxanorbornane lactone-yl (meth)acrylate, a structural unit derived from a cyano-substituted norbornane lactone-yl (meth)acrylate, a structural unit derived from norbornane lactone-yloxycarbonylmethyl (meth)acrylate, a structural unit derived from butyrolactone-3-yl (meth)acrylate, a structural unit derived from 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 the total 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, the adhesion between the resist film formed from the resist composition and the substrate can be further improved.

[0062] When the polymer component contains the [B] polymer and the [B] polymer has the structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to the total structural units constituting the [B] polymer 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 ratio is preferably 70 mol%, more preferably 65 mol%, even more preferably 60 mol%, and particularly preferably 55 mol%. By setting the content ratio 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 determined by gel permeation chromatography (GPC) is not particularly limited, but the lower limit is preferably 1,000, more preferably 2,000, further preferably 3,000, and particularly preferably 5,000. On the other hand, the upper limit of Mw of the polymer [A] is preferably 50,000, more preferably 30,000, further preferably 20,000, and particularly preferably 15,000.

[0066] By setting the Mw of the polymer [A] within the above range, the coating property and the suppression of development defects of the resist composition are improved. If the Mw of the polymer [A] is smaller than the lower limit, the resist film may not have sufficient heat resistance. On the other hand, if the Mw of the polymer [A] is larger than the upper limit, the developability of the resist film may be reduced.

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

[0068] The weight average molecular weight (Mw) of the polymer [B] in terms of polystyrene measured by gel permeation chromatography (GPC) 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 coating property and the suppression of development defects of the resist composition are improved. If the Mw of the polymer [B] is smaller 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 Mw to the polystyrene-equivalent number average molecular weight (Mn) of the polymer (B) measured by GPC is preferably 1. On the other hand, the upper limit of the ratio is preferably 5, more preferably 3, and even more preferably 2.

[0070] In this specification, the Mw and Mn of the polymer are values ​​measured by 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 mass%, more preferably 0.5 mass%, and even more preferably 0.3 mass%. The lower limit of the content is, for example, 0.01 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] In this specification, the content of low molecular weight components in the polymer is a value measured by 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, further preferably 4% by mass, and particularly preferably 7% by mass. Meanwhile, the upper limit of the above content is preferably 60% by mass, more preferably 40% by mass, and further 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 13C-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 a suitable 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 polymerize, 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 polymerize, 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 polymerize.

[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. Among these, the radical polymerization initiator is preferably AIBN and dimethyl 2,2'-azobisisobutyrate, and more preferably AIBN. 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. Meanwhile, 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] It is preferable to recover the polymer [A] and the polymer [B] 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 via energy transfer or electron transfer, thereby causing a reaction of the substrate.

[0080] In the resist composition of the present disclosure, the compounds represented by the above general formulas (1) 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, the 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 above-mentioned polymer component so that the polymer component becomes soluble or insoluble in a developer.

[0083] For example, when the acid generator is irradiated with a first radiation having a wavelength of 300 nm or less and is not irradiated with a second radiation having a wavelength exceeding 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 range of the wavelength of the first radiation is not limited as long as it is 300 nm or less, but is preferably 250 nm or less, 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 the maximum absorption wavelength for the radiation transitioning (or shifting) from the wavelength region of the first radiation to the wavelength region of the second radiation.

[0087] In addition, the acid generator decomposes when irradiated with the second radiation after being irradiated with the first radiation, but does not decompose when irradiated with the second radiation without being irradiated with the first radiation. Here, the case where the second radiation is irradiated without being irradiated with the first radiation indicates a state where only the second radiation is irradiated without being irradiated with the first radiation. In addition, the case where the second radiation is irradiated after being irradiated with the first radiation indicates a state where only the first radiation is irradiated with the second radiation. Furthermore, the decomposition of the acid generator indicates that the acid generator changes 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 becomes more biased and hydrophilicity increases. By increasing the polarity of the acid generator, the solubility of the acid generator in a hydrophilic developer such as an organic alkaline solution increases, while the solubility of the acid generator in a hydrophobic developer such as an organic solvent decreases.

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

[0091] In other words, the acid generator can generate acid when irradiated with the first radiation before the light absorption wavelength changes to absorb the second radiation, whereas the acid generator can generate acid when irradiated with the second radiation after the light absorption wavelength changes to absorb 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 changed 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 two or more other acid generators, regardless of whether it is a polymer component or a low molecular weight component. In addition, in the resist composition, the acid generator may be substituted as a part of the polymer component.

[0097] Other acid generators than the above-mentioned acid generators containing onium salts include general-purpose ionic acid generators and non-ionic acid generators.Ionic acid generators include onium salt compounds such as iodonium salts and sulfonium salts other than the above.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 generators.

[0099] The resist composition of the present disclosure contains a resist base material, a compound represented by any one of the general formulas (1) to (10), and an acid generator (PAG) that generates an acid upon exposure. When the compound represented by any one of the general formulas (1) to (6) absorbs ultraviolet light, it changes to a compound represented by any one 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.

[0100] Furthermore, the compounds represented by the above general formulas (1) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change to the polar compounds represented by the above general formulas (7) to (10). Therefore, by using the above general formulas (1) to (6) as photosensitizer precursors, the compounds represented by the above general formulas (7) to (10) can be easily removed when irradiating with UV all at once in the process 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, it is preferable that a photosensitizer 2 is bonded to an acid generator (PAG) 3. In the example shown in FIG. 5, a non-polar compound represented by the above general formula (6) absorbs ultraviolet light and changes to a polar compound represented by the above general formula (9).

[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 as 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] Thus, 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 is enhanced, and a resist composition containing such a photosensitizer and acid generator can have high functionality as a photosensitizer chemically amplified resist.

[0105] Fig. 6 is a diagram showing the composition of a resist composition (a composition in which a photosensitizer bonds 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, as shown in Fig. 6, a photosensitizer 2 is preferably bonded to a resist base material 1. The examples shown in Figs. 7 to 9 show three examples in which the compound represented by general formula (6) above is bonded to the resist base material (resist polymer) 1 in different ways.

[0107] In the resist composition shown in FIG. 6, the reactivity of each component can be adjusted by the length of the structure in which the resist base material 1 and the photosensitizer 2 are bonded to each other.

[0108] In the example shown in Figure 10, the compound represented by the above general formula (6) bonded to the resist base material 1 is detached from the resist base material 1 upon absorption of ultraviolet light, generating a polar compound represented by the above general formula (9).

[0109] In the example shown in Fig. 11, the compound represented by the above general formula (6) bonded to the resist base material 1 is converted to the polar compound represented by the above 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] Since the photosensitizer is bound to the resist base material 1 in this way, when the acid generator (PAG) is present near the resist base material 1 in the resist composition, the interaction between the resist base material 1, the acid generator (PAG), and the photosensitizer becomes strong. Therefore, a resist composition containing such a photosensitizer and resist base material can have high functionality as a photosensitizer 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)). In the resist composition of the present disclosure, as shown in FIG. 13, it is preferable that an acid generator (PAG) 3 is bound to a resist base material 1, and further a photosensitizer 2 is bound to the acid generator (PAG) 3.

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

[0113] In this way, 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, which increases 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, which increases 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 have even higher functionality as a photosensitizer chemically amplified resist.

[0114] The resist composition of the present disclosure may contain a resist base material, at least one compound represented by the above general formulas (1) to (10), an acid generator (PAG), and a quencher (PDB). The compound represented by the above general formulas (1) to (10) is an example of a photosensitizer in the resist composition containing the quencher of the present disclosure.

[0115] A quencher is also called a photodegradable base (PDB) and has basicity against an acid. A quencher is a component that acts with an acid (e.g., neutralizes) and has a function of suppressing the acid generated from an acid generator. In addition, basicity indicates that it acts as a base relative to an acid. Therefore, a basic quencher is not limited to one that has alkalinity, and also includes a weak acid salt that can become a base against an acid.

[0116] The quencher loses its basicity to an acid when irradiated with the above-mentioned first radiation (radiation having a wavelength of 300 nm or less), for example, and retains its basicity to an acid when irradiated with the above-mentioned 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 an acid when irradiated with only the first radiation. The quencher also loses its basicity to an acid 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 an acid when irradiated with only the second radiation without being irradiated with the first radiation.

[0118] That is, before the light absorption wavelength changes to absorb the second radiation, the quencher loses its basicity to the acid when irradiated with the first radiation, whereas after the light absorption wavelength changes to absorb the second radiation, the quencher loses its basicity to the acid 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, the quencher includes an onium compound that changes 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 WO2018 / 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 based on the mass excluding the polymer main chain.

[0123] In the resist composition according to this embodiment, the quencher may be used alone or in a mixture of two or more kinds, regardless of whether it is a polymer component or a low molecular weight component, or may be used in combination with other quenchers. In addition, in the resist composition, the quencher may be substituted as a part of the polymer component.

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

[0125] When a quencher other than the above quencher 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 quencher.

[0126] In addition, the resist composition according to this embodiment contains a normal solvent (such as an organic solvent) in addition to the above-mentioned polymer component, acid generator, and quencher, 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 one of the above general formulas (1) 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 one of the above general formulas (1) to (6) absorbs ultraviolet light, it changes to a compound represented by any one of the above 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 above general formulas (1) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change to the polar compounds represented by the above general formulas (7) to (10). Therefore, by using the above general formulas (1) to (6) as photosensitizer precursors, the compounds represented by the above general formulas (7) to (10) can be easily removed when irradiating with UV all at once in the process 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 bound to a quencher (PDB)). In the resist composition of the present disclosure, as shown in FIG. 14, a photosensitizer 2 is preferably bound 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 close 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 the length of the structure in which the photosensitizer 2 and the quencher (PDB) 4 are bonded to each other.

[0132] Thus, by binding the photosensitizer to the quencher (PDB) in this manner, the interaction between the photosensitizer and the quencher (PDB) in the resist composition becomes greater, and the resist composition containing such a photosensitizer and quencher (PDB) can have high functionality as a photosensitizer chemically amplified resist.

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

[0134] In the resist composition of the present disclosure, the photosensitizer 2 (a compound represented by the above general formulas (1) 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, 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, it becomes easier to remove the resist base and photosensitizer when they are irradiated with UV light all at once in the process after EUV exposure, which is expected to improve the dissolution contrast.

[0136] Fig. 17 is a diagram showing a conventional process for a photosensitizer chemically amplified resist. Fig. 18 is a diagram showing a process for a photosensitizer chemically amplified resist using the resist composition of the present disclosure.

[0137] Note that FIG. 17 is disclosed to facilitate comparison with FIG. 18, and the arrangement of the components in FIG. 17 is not particularly significant.

[0138] In a conventional photosensitizer chemically amplified resist process, when a resist composition containing a resist base material 1, a photosensitizer precursor (PP) 2, a photoacid generator (PAG) 3, and a quencher (QC) 4 is exposed to EUV on a substrate B, the photosensitizer precursor (PP) 2 changes to an activated photosensitizer (PS) 2' (Figure 17(A)). Next, when the resist composition is developed by a developing device E (Figure 17(B)), only the exposed portion of the resist composition is removed (Figure 17(C)).

[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 of photosensitizer chemically amplified resist using the resist composition of the present disclosure, the compounds represented by the above general formulas (1) to (10) are used as photosensitizers. When the resist composition is exposed to EUV, the photosensitizer precursor (PP) 2 is activated to produce photosensitizer (PS) 2', which is polar and therefore removed by development, thereby improving the dissolution contrast (Figures 18(A) to (C)).

[0141] <Method of producing resist composition> 19 to 21 are diagrams showing embodiments of producing a resist composition according to the present disclosure. In the method of producing a resist composition according to the present disclosure, at least one compound represented by the above general formulas (1) to (10) is mixed into a resist base material.

[0142] For example, a compound represented by any one of the general formulas (1) to (10) 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 (1) to (10) and the resist solution (resist base), and a resist composition (mixed solution 6) in which the resist base (cation) and the photosensitizer (anion) are ionically bonded as shown in FIG. 16 is obtained.

[0143] The method for producing the resist composition (such as 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 (1) to (10) (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 method of producing a resist composition according to the present disclosure, the resist composition is obtained by mixing at least one compound represented by general formulas (1) to (10) with a resist base material, so that the resist composition can be produced easily.

[0145] In addition, in the method for producing a resist composition according to the present disclosure, ion exchange is performed between the resist base material and at least one compound represented by general formulas (1) to (10), and 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 the process after EUV exposure.

[0146] <Substrate Processing Apparatus and Substrate Processing Method> 22 to 25 are diagrams showing examples of substrate processing apparatus using the resist composition of the present disclosure. As shown in Fig. 22, the substrate processing apparatus 10 of the present disclosure has 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 dark chamber 11 is provided in which a substrate B on which a resist film is to be formed is placed. The exposure section 12 exposes the resist composition (a resist composition containing the compounds represented by the general formulas (1) to (10) above as a sensitizer) formed as a film on the substrate B. The development section 13 develops the exposed resist composition.

[0148] The opening and closing window 14 is closed during exposure and development, and is opened when inserting and removing the substrate B before and after processing. Note that the opening and closing window 14 is provided arbitrarily, and the substrate processing apparatus 10 may have a structure provided with an opening and 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 (resist pattern forming method) includes a film forming 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 (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 (radiation having a wavelength of more than 300 nm), a bake step (PEB) 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.

[0150] In addition, the above process may include a patterned post-exposure bake step (PEB) between the patterned exposure step and the flood exposure step, in which the resist film after the patterned exposure step is heated. Furthermore, instead of including the patterned post-exposure bake step (PEB), the bake step (PEB) in which the resist film after the flood 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, and 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, and more preferably 450 nm or less, since 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 (1) to (10) are in the vicinity 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] In the substrate processing apparatus of the present disclosure, a resist composition containing a compound represented by the above general formulas (1) to (10) as a sensitizer is used, and the compound represented by the above general formulas (1) to (6) is converted to a compound represented by the above general formulas (7) to (10) by absorbing ultraviolet light, and the absorption wavelength becomes longer. Therefore, the compound represented by the above general formulas (1) to (10) may be unexpectedly activated when exposed to visible light (short-wavelength visible light) close to ultraviolet light. Therefore, in the substrate processing apparatus of the present disclosure, exposure by ultraviolet light irradiation and development 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 the above general formulas (1) to (10) is used. As described above, the compounds represented by the above general formulas (1) to (6) (compounds having a xanthylium structure, an acridinium structure, or an anthracene structure) and the like change to the compounds represented by the above general formulas (7) to (10) by absorbing ultraviolet light, respectively, and the absorption wavelength becomes longer. Therefore, by using the compounds represented by the above general formulas (1) to (6) and the like as a photosensitizer precursor, the photosensitizer that has changed to the compound represented by the above general formulas (7) to (10) can be treated with ultraviolet light close to visible light when UV is irradiated all at once in the process after EUV exposure.

[0155] In addition, as described above, the compounds represented by the above general formulas (1) to (6) are non-polar before absorbing ultraviolet light, but after absorbing ultraviolet light, they change into the polar compounds represented by the above general formulas (7) to (10), respectively. Therefore, when UV light is irradiated all at once in the process after EUV exposure, it becomes easy to remove the compounds represented by the above general formulas (7) to (10), and an improvement in dissolution contrast can be expected.

[0156] 23, the substrate processing apparatus 20 of the present disclosure has an infrared monitor. The form of the infrared monitor is not particularly limited, but may be, for example, composed of 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 above general formulas (1) to (10) contained as sensitizers in the resist composition may be unexpectedly activated when exposed to visible light (short-wavelength visible light) close to ultraviolet light. Therefore, in the substrate processing apparatus of the present disclosure, an infrared monitor is provided in the darkroom to prevent exposure to short-wavelength visible light, and substrate processing can be monitored even in such a darkroom.

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

[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 embodiment of the flow path 32 is not limited thereto, and the latent photosensitizer (photosensitizer precursor) solution may flow through the flow path 32A, and the resist solution may flow through the flow path 32B.

[0160] Nozzle 33 is disposed above coating section 31 and communicates with the tip of flow path 32. In substrate processing apparatus 30 of the present disclosure, the resist composition mixed in flow path 32 is discharged from nozzle 33 and coated onto substrate B. This makes it possible to carry out the above-mentioned method for producing a resist composition (mixing at least one compound represented by the above general formulas (1) to (10) into a resist base material).

[0161] 25, a substrate processing apparatus 40 of 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 flow path 42B branching therefrom. 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 of the present disclosure.

[0162] The flow path 42B communicates with 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 caused to flow through 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 communicates with 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 vulnerable 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, so that the inside of the flow path 42 is replaced with an alkaline solution beforehand before the resist composition is flowed, thereby preventing deterioration of the resist composition due to acid.

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

[0166] (Appendix 1) A resist composition comprising at least one compound represented by the following general formulas (1) to (3): [ka] [In the general formula (1), R1 to R4 each independently represent 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; X1 and Y1 each independently represent one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [ka] [In the general formula (2), R5 to R9 each independently represent 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; X2 is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y2 is any one selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. [ka] [In general formula (3), R 10 ~R 15 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; X3 is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom; Y3 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 comprising a compound represented by the following general formula (4): [ka] [In the general formula (4), R1 to R4 each independently represent 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; X1 and Y1 each independently represent 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 comprising a compound represented by the following general formula (5): [ka] [In the general formula (5), R5 to R9 each independently represent 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; X2 is any one selected from the group consisting of a nitrogen atom, a phosphorus atom, an arsenic atom, and an antimony atom; Y2 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 comprising a compound represented by the following general formula (6): [ka] [In the general formula (6), R5 to R9 each independently represent 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; Y2 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 comprising a compound represented by the following general formula (7): [ka] [In the general formula (7), R1 to R4 each independently represent 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; X1 is an oxygen atom or a sulfur atom.

[0171] (Appendix 6) A resist composition comprising a compound represented by the following general formula (8): [ka] [In the general formula (8), R5 to R9 each independently represent 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; X2 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 comprising a compound represented by the following general formula (9): [ka] [In general formula (9), R5 to 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.]

[0173] (Appendix 8) A resist composition comprising a compound represented by the following general formula (10): [ka] [In general formula (10), R 10 ~R 14 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; X3 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) A resist base material; At least one compound represented by the general formulas (1) to (10), The resist composition according to any one of claims 1 to 8, further comprising an acid generator that generates an acid upon exposure to light.

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

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

[0177] (Appendix 12) the acid generator is bound to the resist substrate; 12. The resist composition according to any one of claims 9 to 11, wherein the compound is bound to the acid generator.

[0178] (Appendix 13) A resist base material; At least one compound represented by the general formulas (1) to (10), an acid generator that generates an acid upon exposure to light; 13. The resist composition according to any one of claims 1 to 12, further comprising a quencher having basicity against an acid.

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

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

[0181] (Appendix 16) A method for producing the resist composition according to any one of claims 1 to 15, comprising the steps of: A method for producing a resist composition, which comprises mixing at least one compound represented by the above general formulas (1) to (10) with a resist base material.

[0182] (Appendix 17) 17. The method for producing a resist composition according to claim 16, further comprising the step of: conducting ion exchange between the resist base material and the compound.

[0183] (Appendix 18) a darkroom in which the substrate is placed; an exposure unit that is provided in the darkroom and exposes the resist composition according to any one of appendixes 1 to 15 that is formed as a film on the substrate; a developing section provided in the darkroom for developing the exposed resist composition.

[0184] (Appendix 19) a nozzle for discharging the resist composition; a first flow path communicating with the nozzle and through which the resist composition flows; 20. The substrate processing apparatus according to claim 18, further comprising: a second flow path communicating with the first flow path and through which an alkaline solution flows.

[0185] (Appendix 20) A film forming step of forming a resist film on a substrate, the resist film comprising the resist composition according to any one of claims 1 to 15; a pattern exposure step of irradiating the resist film with radiation having a wavelength of 300 nm or less through a mask; a floodwise exposure step of irradiating the resist film after the patternwise exposure step with radiation having a wavelength exceeding 300 nm; a baking step of heating the resist film after the floodwise exposure step; and contacting the resist film after the baking 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. [Explanation of symbols]

[0187] 1. Resist substrate 2. Photosensitizers (photosensitizer precursors) 2´ Photosensitizer (activated photosensitizer) 3. Acid Generator (PAG) 4 Quencher (PDB) B Substrate E Developing device A container C outlet 6 Mixed liquid 6´ Film 10, 20, 30, 40 Substrate processing apparatus 11, 21 Darkroom 12, 22 Exposure section 13, 23 Development section 14 Opening and closing windows 24 Infrared lamp 25 Infrared Camera 31, 41 Application part 32, 32A, 32B, 42, 42A, 42B flow path 33, 43 nozzle

Claims

1. A resist composition comprising at least one compound represented by the following general formulas (1) to (3): 【Chemistry 1】 [In general formula (1), R １ ~R ４ 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; X 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. 【Chemistry 2】 [In general formula (2), 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; X 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. 【Chemistry 3】 [In general formula (3), R １０ ~R １５ 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; X ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin 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.

2. A resist composition comprising a compound represented by the following general formula (4): 【Chemistry 4】 [In general formula (4), R １ ~R ４ 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; X 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 comprising a compound represented by the following general formula (5): 【Chemistry 5】 [In general formula (5), 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; X 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.

4. A resist composition comprising a compound represented by the following general formula (6): 【Chemistry 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; Y 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 comprising a compound represented by the following general formula (7): 【Chemistry 7】 [In general formula (7), R １ ~R ４ 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; X １ is an oxygen atom or a sulfur atom.

6. A resist composition comprising a compound represented by the following general formula (8): 【Chemistry 8】 [In general formula (8), 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; X 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 comprising a compound represented by the following general formula (9): 【Chemistry 9】 [In general formula (9), 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.

8. A resist composition comprising a compound represented by the following general formula (10): 【Chemistry 10】 [In general formula (10), R １０ ~R １４ 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; X ３ is any one selected from the group consisting of a carbon atom, a silicon atom, a germanium atom, and a tin atom.

9. A resist base material; At least one compound represented by the general formulas (1) to (10), The resist composition according to claim 1 , further comprising an acid generator that generates an acid upon exposure to light.

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

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

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

13. A resist base material; At least one compound represented by the general formulas (1) to (10), an acid generator that generates an acid upon exposure to light; The resist composition according to claim 1 , further comprising a quencher having basicity against 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 the compound is ionically bonded to the resist base material.

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

17. The method for producing a resist composition according to claim 16, wherein the resist base material is subjected to ion exchange with the compound.

18. a darkroom in which the substrate is placed; an exposure section that is provided in the darkroom and exposes the resist composition according to claim 1 formed as a film on the substrate; a developing section provided in the darkroom for developing the exposed resist composition.

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

20. A film forming step of forming a resist film containing the resist composition according to claim 1 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 floodwise exposure step of irradiating the resist film after the patternwise exposure step with radiation having a wavelength exceeding 300 nm; a baking step of heating the resist film after the floodwise exposure step; and contacting the resist film after the baking step with a developer.

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