Polymerizable monomer, high molecular compound, chemically amplified resist composition, and pattern forming method

Abstract

This invention relates to polymerizable monomers, polymeric compounds, chemically amplified resist compositions, and patterning methods. The objectives of this invention are: to provide chemically amplified resist compositions that offer superior sensitivity and resolution compared to conventional positive resist materials, small LWR or dimensional variation, and excellent process windows; polymeric compounds contained in the aforementioned chemically amplified resist compositions; polymerizable monomers used in the aforementioned polymeric compounds; and patterning methods using the aforementioned compositions. This invention relates to a polymerizable monomer characterized by having one or more acid-labile groups with different structures.

Description

Technical Field

[0001] This invention relates to polymerizable monomers, polymeric compounds, chemically amplified resist compositions, and methods for pattern formation. Background Technology

[0002] With the increasing integration and speed of LSI (Lithium-ion Sensors), the miniaturization of patterned regularity is progressing rapidly. This is driven by the widespread adoption of 5G high-speed communication and artificial intelligence (AI), which necessitates high-performance devices to process these technologies. Regarding state-of-the-art miniaturization technology, mass production of 5nm node devices using 13.5nm extreme ultraviolet (EUV) lithography has been achieved. Furthermore, research is underway on EUV lithography for the next generation of 3nm node devices and the generation after that, at the 2nm node.

[0003] As miniaturization progresses, image blurring caused by acid diffusion becomes a problem. To ensure resolution of fine patterns smaller than 45 nm, it has been suggested that in addition to the previously recommended improvement of dissolution contrast, control of acid diffusion is also important. However, since chemically amplified resist materials enhance sensitivity and contrast through acid diffusion, reducing the post-exposure baking (PEB) temperature or shortening the baking time to suppress acid diffusion to the limit will significantly reduce sensitivity and contrast.

[0004] This illustrates the triangular trade-off between sensitivity, resolution, and linewidth roughness (LWR). To improve resolution, acid diffusion needs to be suppressed, but if the acid diffusion distance is shortened, sensitivity will decrease.

[0005] Adding an acid-generating agent that produces a bulky acid is effective in suppressing acid diffusion. Therefore, it has been suggested that the polymer contain repeating units from onium salts with polymerizable unsaturated bonds. In this case, the polymer also functions as an acid-generating agent (polymer-bonded acid-generating agent). Patent Document 1 suggests sulfonium salts and sulfonium salts with polymerizable unsaturated bonds that produce specific sulfonic acids. Patent Document 2 suggests sulfonium salts in which sulfonic acids are directly bonded to the main chain.

[0006] With the further miniaturization of resist patterns, extreme ultraviolet (EUV) and electron beams are now used as exposure light sources. However, challenges have emerged that cannot be solved solely by suppressing acid diffusion. One such challenge is the improvement of the process window. Due to the miniaturization of patterns, even slight changes in exposure and development conditions have a greater impact on the shape of the resist pattern and the generation of defects. There is a need for radiation-sensitive resin compositions with a wide process window that can absorb such slight changes in processing conditions. For example, when forming line and space patterns using positive resists, the line width of the pattern narrows as the exposure amount increases, but it is preferable for the pattern to maintain its shape without collapsing or becoming damaged. On the other hand, in areas with low exposure, it is desirable to maintain the line and space pattern without bridging between patterns. However, the aforementioned conventional radiation-sensitive resin compositions do not meet the requirement of a sufficient process window.

[0007] Existing technical documents

[0008] Patent documents

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2006-045311

[0010] [Patent Document 2] Japanese Patent Application Publication No. 2006-178317 Summary of the Invention

[0011] [The problem that the invention aims to solve]

[0012] The present invention is made in view of the foregoing circumstances, and its object is particularly to provide a chemically amplified resist composition having superior sensitivity and resolution compared to conventional positive resist materials, small LWR or dimensional variation, and providing an excellent process window, a polymeric compound contained in the aforementioned chemically amplified resist composition, a polymeric monomer used in the aforementioned polymeric compound, and a patterning method using the aforementioned composition.

[0013] [Methods for solving the problem]

[0014] To address the aforementioned issues, the present invention provides a polymerizable monomer having one or more acid-indestructible groups with different structures.

[0015] If the polymeric monomer of the present invention is used, the chemically amplified resist composition containing the polymeric compound using it will have a sensitivity and resolution superior to conventional positive resist materials, with small LWR or size variation, and will provide an excellent process window.

[0016] Furthermore, in this invention, it is preferable that the aforementioned polymerizable monomer is represented by the following general formula (A1).

[0017] [Chemistry 1]

[0018]

[0019] In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 It is a single bond or an aryl group; n is 0 or 1; AL 1 and AL 2 It is an unstable group in acids; however, AL 1 With AL 2 They have different structures.

[0020] In this invention, such polymerizable monomers are preferred.

[0021] In this case, it is more ideal for the polymerizable monomer of the aforementioned general formula (A1) to be represented by the following general formula (A1-1) or (A1-2).

[0022] [Chemistry 2]

[0023]

[0024] In the formula, R A X 1 , n, and AL 2 Same as above; R 11 R 21 and R 22 Each group can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may contain heteroatoms; W1 represents an alicyclic hydrocarbon group; W2 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0025] In this invention, such polymerizable monomers are even more preferred.

[0026] In this case, it is preferable that the polymerizable monomer of the aforementioned general formula (A1-1) is represented by any one of the following general formulas (A2-1) and (A2-2), and that the polymerizable monomer of the general formula (A1-2) is represented by any one of the following general formulas (A2-3) and (A2-4).

[0027] [Chemistry 3]

[0028]

[0029] In the formula, R A X 1 R 11 R 21 R 22 W1 and W2 are the same as described above; R 12 R 13 R 14 R23 R 24 and R 25 Each is independently a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may also contain heteroatoms; W'11 and W'21 each independently represent an alicyclic hydrocarbon group; W'12 and W'22 each independently represent an alicyclic hydrocarbon group or an aromatic hydrocarbon group; m is 0 or 1; but when W2 is an alicyclic hydrocarbon group, m is 1; when W2 is an aromatic hydrocarbon group, m is 0 or 1.

[0030] In this invention, such polymerizable monomers are preferred.

[0031] Furthermore, the present invention provides a polymer compound containing repeating units obtained from the polymerizable monomers described above.

[0032] If it is such a polymer compound, then the chemically amplified resist composition containing it will have a sensitivity and resolution superior to previous positive resist materials, with small LWR or size variation, and will provide an excellent process window.

[0033] At this point, it is more ideal for the aforementioned polymeric compound to also contain repeating units represented by the following general formula (b1).

[0034] [Chemistry 4]

[0035]

[0036] In the formula, R A Y is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; 1 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom in the main chain; R 30 It can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; b is an integer from 1 to 4; c is an integer from 0 to 4; but, 1≤b+c≤5.

[0037] In this invention, it is ideal for the polymer compound to have such repeating units.

[0038] Furthermore, in this invention, it is preferable that the aforementioned polymeric compound also contains at least one of the repeating units represented by the following general formula (c1), the following general formula (c2), the following general formula (c3), and the following general formula (c4).

[0039] [Chemistry 5]

[0040]

[0041] In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 It is a single bond or a phenylene; Z 2 For *-C(=O)-OZ 21 -、*-C(=O)-NH-Z 21 - or *-OZ 21 -;Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 3 Each can be independently a single bond, phenylene, naphthylene, or *-C(=O)-OZ 31 -;Z 31 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms; the aforementioned aliphatic hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; Z 4 Each is independently a single bond, **-Z 41 -C(=O)-O-、**-C(=O)-NH-Z 41 - or **-OZ 41 -;Z 41 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 5 Each is independently a single bond, ***-Z 51 -C(=O)-O-、***-C(=O)-NH-Z 51 - or ***-OZ 51 -;Z 51 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 6 It can be a single bond, methylene, ethylene, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, *-C(=O)-OZ 61 -、*-C(=O)-NH-Z 61 - or *-OZ 61 -;Z 61 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; * indicates an atomic bond with a carbon atom in the main chain; ** indicates an atomic bond with a Z atom. 3 atomic bonds; *** indicates the relationship with Z 4 atomic bonds; R 31 and R 32 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; furthermore, R 31 With R 32They can also bond to each other and form rings together with the sulfur atoms they are bonded to; L 1 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, carbonate bond, or carbamate bond; Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; however, it does not contain all Rf atoms. 5 and Rf 6 The case where both are hydrogen atoms; M - It is a non-nucleophilic relative ion; A + It is an onium cation; d is an integer from 0 to 3.

[0042] In this invention, it is ideal for the polymer compound to have such repeating units.

[0043] Furthermore, this invention provides a chemically amplified resist composition, characterized in that it contains a base resin composed of the polymeric compounds described above, and an organic solvent.

[0044] Such a chemically amplified resist composition would have superior sensitivity and resolution compared to previous positive resist materials, with smaller LWR or dimensional variations, and would provide an excellent process window.

[0045] At this point, it is ideal for the aforementioned chemically amplified resist composition to also contain one or more of the following: quenching agent, photoacid generator, and surfactant.

[0046] The chemically amplified resist composition of the present invention may contain these additives.

[0047] Furthermore, the present invention provides a pattern forming method comprising the following steps: forming a resist film on a substrate using the chemically amplified resist composition described above; exposing the aforementioned resist film to high-energy radiation; and developing the aforementioned exposed resist film using a developing solution.

[0048] Such a patterning method can provide a patterning method using chemically amplified resist compositions that have superior sensitivity and resolution compared to conventional positive resist materials, small LWR or dimensional variation, and provide an excellent process window.

[0049] At this point, using KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet rays with wavelengths of 3–15 nm as the aforementioned high-energy rays is more ideal.

[0050] In this invention, such high-energy rays can be used.

[0051] [The effects of the invention]

[0052] As described above, when patterning is performed using a chemically amplified resist composition containing a polymeric compound with polymeric monomers of the present invention as the base resin, it is possible to form resist patterns with high contrast, good sensitivity, and excellent photolithographic properties such as LWR and process windows. Detailed Implementation

[0053] As mentioned above, there is a particular need to develop chemically amplified resist compositions that have superior sensitivity and resolution compared to previous positive resist materials, low dimensional variation (LWR) or small size variation, and provide excellent process windows; polymeric compounds contained in the aforementioned chemically amplified resist compositions; polymeric monomers used in the aforementioned polymeric compounds; and patterning methods using the aforementioned compositions.

[0054] In order to achieve the aforementioned objectives, the inventors conducted repeated and careful research and discovered that using a polymeric monomer with a specific structure as the base resin in a chemically amplified resist composition results in high sensitivity and high contrast, excellent photolithography performance such as LWR and process windows, and is extremely effective in the formation of fine patterns, thus leading to the completion of this invention.

[0055] That is, the present invention is a polymerizable monomer having one or more acid-indestructible groups with different structures.

[0056] The present invention will now be described in detail, but the invention is not limited thereto.

[0057] [Polymerizable monomers]

[0058] The polymerizable monomers of the present invention are those having one or more acid-labile groups with different structures. By having one or more acid-labile groups with different structures within a single molecule, the contrast between dissolution before and after deprotection due to acid increases, thereby improving resolution. Japanese Patent Application Publication No. 2017-019911 also describes materials having multiple acid-labile groups, but it only illustrates compounds having multiple acid-labile groups with the same structure. In this case, the impact of undesired reactions in unexposed areas caused by acid diffusion is significant, leading to degradation of resolution and LWR. On the other hand, because the polymerizable monomers of the present invention have acid-labile groups with different reactivity, even if such undesired reactions occur in the boundary region, the probability of multiple acid-labile groups being deprotected simultaneously is low, and it is presumed that their photolithography performance will not deteriorate.

[0059] Ideally, the polymerizable monomers of the present invention should be represented by the following general formula (A1).

[0060] [Chemistry 6]

[0061]

[0062] (where R is in the formula) A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 It is a single bond or an aryl group. n is 0 or 1. AL 1 and AL 2 It is an unstable group in acids. However, AL 1 With AL 2 These are different structures.

[0063] In the above general formula (A1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 It can be a single bond or an arylene group. Specific examples of arylene groups include phenylene, naphthylene, and anthracene. n is 0 or 1. AL 1 and AL 2 Each is an unstable group in acid. However, AL 1 With AL 2 These are different structures. Specific examples of the aforementioned acid-instable groups include those described in Japanese Patent Application Publication Nos. 2013-080033 and 2013-083821.

[0064] Generally speaking, specific examples of the aforementioned unstable acid groups can be listed by the following general formulas (AL-1) to (AL-3).

[0065] [Chemistry 7]

[0066]

[0067] (In the formula, * represents an atomic bond.)

[0068] In the above general formulas (AL-1) and (AL-2), R L1 and R L2 Each hydrocarbon group is independently composed of 1 to 40 carbon atoms and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, the hydrocarbon groups have 1 to 20 carbon atoms.

[0069] In the above general formula (AL-1), a2 is an integer from 0 to 10, preferably an integer from 1 to 5.

[0070] In the above general formula (AL-2), R L3 and R L4Each group is independently composed of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Of the aforementioned hydrocarbon groups, those having 1 to 20 carbon atoms are preferred. Furthermore, R... L2 R L3 and R L4 Any two of them can also bond to each other and together with the carbon atoms they are bonded to, or carbon atoms and oxygen atoms, to form a ring with 3 to 20 carbon atoms. Of the aforementioned rings, a ring with 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0071] In the above general formula (AL-3), R L5 R L6 and R L7 Each group is an independent hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Of the aforementioned hydrocarbon groups, those having 1 to 20 carbon atoms are preferred. Furthermore, R... L5 R L6 and R L7 Any two of them can also bond to each other and together with the carbon atoms they are bonded to form a ring with 3 to 20 carbon atoms. Of the aforementioned rings, a ring with 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0072] Regarding the structures of other acid-indestructible groups, examples include those described in paragraphs

[0064] to

[0068] of Japanese Patent Application Publication No. 2023-123222 and those described in paragraphs

[0013] to

[0014] of Japanese Patent Publication No. 7492842. These are driven by the formation of conjugated olefins or acrylate derivatives after acid desorption reactions.

[0073] In this invention, it is preferable that the polymerizable monomer of the aforementioned general formula (A1) is represented by the following general formula (A1-1) or (A1-2).

[0074] [Chemistry 8]

[0075]

[0076] (where R is in the formula) A X 1 , n, and AL 2 Same as above. R 11 R 21 and R 22 Each group is an independent halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may also contain heteroatoms. W1 represents an alicyclic hydrocarbon group. W2 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0077] In the above general formulas (A1-1) and (A1-2), R A X 1 AL 2 , and n are the same as described above. R 11 R 21 and R 22 Each group is independently a halogen atom, hydroxyl group, nitro group, or may contain heteroatoms and has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms. Specific examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, etc., which are alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.]

[0078] W1 represents an alicyclic hydrocarbon group. W2 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group. Specifically, alicyclic hydrocarbon groups of W1 and W2 can include cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 The cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl, and the aromatic hydrocarbon groups of W2, specifically include aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned cyclic saturated hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned cyclic saturated hydrocarbon groups can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, the cyclic hydrocarbon groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc.

[0079] In this invention, the polymerizable monomer of the aforementioned general formula (A1-1) is represented by any one of the following general formulas (A2-1) and (A2-2), and it is more desirable that the polymerizable monomer of the general formula (A1-2) is represented by any one of the following general formulas (A2-3) and (A2-4).

[0080] [Chemistry 9]

[0081]

[0082] (where R is in the formula) A X 1 R 11 R 21 R 22 W1 and W2 are the same as described above. 12 R 13 R 14 R 23 R 24 and R 25 Each group is independently a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms. W'11 and W'21 each independently represent an alicyclic hydrocarbon group. W'12 and W'22 each independently represent an alicyclic hydrocarbon group or an aromatic hydrocarbon group. m is 0 or 1. However, when W2 is an alicyclic hydrocarbon group, m is 1. When W2 is an aromatic hydrocarbon group, m is 0 or 1.

[0083] In the above general formulas (A2-1) to (A2-4), R A X 1 R 11 R 21 R 22 W1 and W2 are the same as described above. 12 R 13 R 14 R 23 R 24 and R 25 Each group independently represents a halogen atom, a hydroxyl group, a nitro group, or a hydrocarbon group with 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and may also contain heteroatoms. Specifically, it is associated with the group already defined in R. 11 The hydrocarbon groups shown in the examples are the same.

[0084] W'11 and W'21 each independently represent an alicyclic hydrocarbon group, specifically the same as those exemplified in W1. W'12 and W'22 each independently represent an alicyclic hydrocarbon group or an aromatic hydrocarbon group, specifically the same as those exemplified in W2. m is 0 or 1. However, when W2 is an alicyclic hydrocarbon group, m is 1. When W2 is an aromatic hydrocarbon group, m is 0 or 1.

[0085] Regarding the polymerizable monomers of the present invention, the following examples are provided, but the invention is not limited to these.

[0086] [Chemistry 10]

[0087]

[0088] [Chemistry 11]

[0089]

[0090] [Chemistry 12]

[0091]

[0092] The polymerizable monomers of the present invention can be synthesized using methods that fully utilize known organic synthesis techniques.

[0093] The particularly desirable structure of the polymerizable monomer of the present invention is that which has a plurality of cyclic groups as represented by the above general formulas (A2-1) to (A2-4), and the reasons for this can be listed as follows.

[0094] In the repeating units obtained from polymerizable monomers represented by the above-described general formulas (A2-1) to (A2-4) of the present invention contained in the base resin, the bulky acid-instable sites having multiple cyclic groups are removed by exposure, thus increasing the difference in solubility contrast in the polymer before and after deprotection, which is believed to contribute to improved resolution. Similarly, resist compositions having bulky acid-instable groups with polycyclic hydrocarbons are known (e.g., methacrylate-3-ethyl-3-external tetracyclic [4.4.0.1] described in paragraph

[0111] of Japanese Patent Application Publication No. 2005-320516). 2,5 .1 7 ,10 (e.g., dodecyl esters). However, in the case of such acid-labile groups, due to the high molecular weight and hydrophobicity of the deprotected compounds, they become residues after alkaline development. As a result, in positive resists, bridging defects appear on the underexposed side, deteriorating the process window. On the other hand, the polymerizable monomers of the present invention, because the deprotected compounds are further decomposed by acid, ultimately become low molecular weight and low hydrophobic compounds. It is believed that these can be effectively removed by alkaline development, thus widening the process window.

[0095] Furthermore, regarding the unexposed portion, due to its highly hydrophobic structure, it exhibits high resistance to alkali development, resulting in fewer defects (breakage) on the overexposed side. In other words, the chemically amplified resist composition using a polymeric compound obtained from the polymerizable monomers of this invention offers wider tolerance on both the overexposed and underexposed sides, significantly improving the process window, making it suitable as a positive resist material for the formation of fine patterns.

[0096] [Chemical amplification resist composition]

[0097] The chemically amplified resist composition of the present invention comprises: a base resin consisting of a polymeric compound containing repeating units derived from (A) the polymeric monomers of the present invention, and (B) an organic solvent.

[0098] The chemically amplified resist composition of the present invention may, as needed, further contain (C) a quencher, (D) a photoacid generator, and (E) a surfactant; furthermore, it may, as needed, contain (F) other components. That is, it is preferable that the aforementioned chemically amplified resist composition also contains one or more selected from quenchers, photoacid generators, and surfactants.

[0099] [(A) Base Resin]

[0100] The (A) base resin contained in the chemically amplified resist composition of the present invention is a polymeric compound comprising repeating units obtained from the polymeric monomers of the present invention.

[0101] [Polymer compounds]

[0102] The polymeric compound of the present invention contains repeating units obtained from the polymerizable monomers described above. The aforementioned polymerizable monomers can ideally be used as constituent units (hereinafter also referred to as repeating unit A) of the polymeric compound that forms the base resin (A) in the chemically amplified resist composition of the present invention.

[0103] Regarding repeating unit A, two or more different polymerizable monomers can also be copolymerized as the constituent unit of a polymer compound.

[0104] The aforementioned polymeric compounds are more preferably those that also contain repeating units represented by the following general formula (b1) (hereinafter also referred to as repeating unit b1).

[0105] [Chemistry 13]

[0106]

[0107] (where R is in the formula) A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain. R 30The radical can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. b is an integer from 1 to 4. c is an integer from 0 to 4. However, 1 ≤ b + c ≤ 5.

[0108] In the above general formula (b1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain. R 30 The radical can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. b is an integer from 1 to 4. c is an integer from 0 to 4. However, 1 ≤ b + c ≤ 5.

[0109] Regarding specific examples of the repeating unit b1, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[0110] [Chemistry 14]

[0111]

[0112] [Chemistry 15]

[0113]

[0114] [Chemistry 16]

[0115]

[0116] [Chemistry 17]

[0117]

[0118] [Chemistry 18]

[0119]

[0120] The aforementioned polymeric compounds are more preferably those that also contain repeating units represented by the following general formula (b2) (hereinafter also referred to as repeating unit b2).

[0121] [Chemistry 19]

[0122]

[0123] In the above general formula (b2), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 40 It is a hydrogen atom, or a group containing at least one of the following structures with 1 to 20 carbon atoms: hydroxyl group other than phenolic hydroxyl group, cyano group, carbonyl group, carboxyl group, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sulcinolone ring, and carboxylic anhydride (-C(=O)-OC(=O)-).

[0124] Regarding specific examples of the repeating unit b2, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[0125] [Chemistry 20]

[0126]

[0127] [Chemistry 21]

[0128]

[0129] [Chemistry 22]

[0130]

[0131] [Chemistry 23]

[0132]

[0133] [Chemistry 24]

[0134]

[0135] [Chemistry 25]

[0136]

[0137] [Chemistry 26]

[0138]

[0139] [Chemistry 27]

[0140]

[0141] [Chemistry 28]

[0142]

[0143] [Chemistry 29]

[0144]

[0145] [Chemistry 30]

[0146]

[0147] [Chemistry 31]

[0148]

[0149] [Chemistry 32]

[0150]

[0151] [Chemistry 33]

[0152]

[0153] [Chemistry 34]

[0154]

[0155] [Chemistry 35]

[0156]

[0157] The repeating unit b1 is particularly suitable for use in EB lithography and EUV lithography. As for the repeating unit b2, in KrF lithography and ArF lithography, it is particularly suitable to have a lactone ring as a polar group.

[0158] The aforementioned polymeric compound may also contain at least one repeating unit selected from the following general formula (c1) (hereinafter also referred to as repeating unit c1.), the following general formula (c2) (hereinafter also referred to as repeating unit c2.), the following general formula (c3) (hereinafter also referred to as repeating unit c3.), and the following general formula (c4) (hereinafter also referred to as repeating unit c4.). These repeating units function as photoacid generators bonded to the polymer backbone.

[0159] [Chemistry 36]

[0160]

[0161] (where R is in the formula) A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or a phenylene oxide. Z 2 For *-C(=O)-OZ 21 -、*-C(=O)-NH-Z 21 - or *-OZ 21 -. Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. 3Each can be independently a single bond, phenylene, naphthylene, or *-C(=O)-OZ 31 -. Z 31 It is an aliphatic alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. The aforementioned aliphatic alkylene groups may also contain hydroxyl groups, ether bonds, ester bonds, or lactone rings. 4 Each is independently a single bond, **-Z 41 -C(=O)-O-、**-C(=O)-NH-Z 41 - or **-OZ 41 -. Z 41 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Z 5 Each is independently a single bond, ***-Z 51 -C(=O)-O-、***-C(=O)-NH-Z 51 - or ***-OZ 51 -. Z 51 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Z 6 It can be a single bond, methylene, ethylene, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, *-C(=O)-OZ 61 -、*-C(=O)-NH-Z 61 - or *-OZ 61 -. Z 61 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. * indicates an atomic bond with a carbon atom in the main chain. ** indicates an atomic bond with Z. 3 Atomic bonds. *** indicates the relationship with Z. 4 Atomic bonds. R 31 and R 32 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. Also, R 31 With R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. L 1 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, carbonate bond, or carbamate bond. Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, not all Rf groups are present. 5 and Rf 6The case where both are hydrogen atoms. M - It is a non-nucleophilic relative ion. A + It is an onium cation. d is an integer from 0 to 3.

[0162] In the above general formulas (c1) to (c4), R A Each can be independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 It is a single bond or a phenylene oxide. Z 2 For *-C(=O)-OZ 21 -、*-C(=O)-NH-Z 21 - or *-OZ 21 -. Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. 3 Each can be independently a single bond, phenylene, naphthylene, or *-C(=O)-OZ 31 -. Z 31 It is an aliphatic alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. The aforementioned aliphatic alkylene groups may also contain hydroxyl groups, ether bonds, ester bonds, or lactone rings. 4 Each is independently a single bond, **-Z 41 -C(=O)-O-、**-C(=O)-NH-Z 41 - or **-OZ 41 -. Z 41 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Z 5 Each is independently a single bond, ***-Z 51 -C(=O)-O-、***-C(=O)-NH-Z 51 - or ***-OZ 51 -. Z 51 It can also contain heteroatoms and is a hydrocarbon group with 1 to 20 carbon atoms. Z 6 It can be a single bond, methylene, ethylene, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, *-C(=O)-OZ 61 -、*-C(=O)-NH-Z 61 - or *-OZ 61 -. Z 61 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group. * indicates an atomic bond with a carbon atom in the main chain. ** indicates an atomic bond with Z. 3 Atomic bonds. *** indicates the relationship with Z. 4 Atomic bonds.

[0163] Z21 Z 31 and Z 61 The aliphatic alkyl sub-group can be any of the following: linear, branched, or cyclic. Specific examples include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl, hexane-1,6-diyl, etc.; cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, etc.; and groups obtained by combining them.

[0164] Z 41 and Z 51 The alkylene group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are listed below, but are not limited to these.

[0165] [Chemistry 37]

[0166]

[0167] (In the formula, the dashed lines represent atomic bonds.)

[0168] In the above general formula (c1), R 31 and R 32Each of the aforementioned hydrocarbon groups can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norcamphenyl, and adamantyl; alkenyl groups with 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups with 6 to 20 carbon atoms, such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these, preferably aryl. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonolactone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0169] Also, R 31 With R 32 They can also bond to each other and form rings together with the sulfur atoms to which they are bonded. In this case, for the aforementioned rings, examples such as R, as exemplified in the description of the general formula (cation-1) described later, can be listed. ct1 and R ct2 Those that can bond together and form rings with the sulfur atoms they are bonded to are the same as those that form rings.

[0170] Specific examples of the cation in repeating unit c1 can be listed below, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[0171] [Chemistry 38]

[0172]

[0173] [Chemistry 39]

[0174]

[0175] [Chemistry 40]

[0176]

[0177] [Chemistry 41]

[0178]

[0179] [Chemistry 42]

[0180]

[0181] [Chemistry 43]

[0182]

[0183] [Chemistry 44]

[0184]

[0185] In the above general formula (c1), M - The ion is a non-nucleophilic relative ion. Among the aforementioned non-nucleophilic relative ions, halide ions, sulfonic acid anions, imide acid anions, and methylated acid anions are preferred. Specific examples of halide ions include chloride ions and bromide ions. Specific examples of sulfonic acid anions (sulfonate ions) include trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, nonafluorobutanesulfonate ions, and other fluoroalkyl sulfonate ions; toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, 1,2,3,4,5-pentafluorobenzenesulfonate ions, and other aryl sulfonate ions; methanesulfonate ions, butanesulfonate ions, and other alkyl sulfonate ions. Specific examples of the aforementioned imide acid anions (imide ions) include bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, and bis(perfluorobutylsulfonyl)imide ions. Specific examples of the aforementioned methylated acid anions (methylated ions) include tris(trifluoromethylsulfonyl)methylated ions and tris(perfluoroethylsulfonyl)methylated ions.

[0186] As for other examples of the aforementioned non-nucleophilic relative ions, anions represented by any of the following general formulas (c1-1) to (c1-4) can be listed.

[0187] [Chemistry 45]

[0188]

[0189] In the above general formula (c1-1), R fa A hydrocarbon group consisting of 1 to 40 carbon atoms, which may be a fluorine atom or may contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. For specific examples, R in the general formula (c1-1-1) described later can be listed and illustrated. fa1 Those representing hydrocarbon groups are the same.

[0190] For the anion represented by the above general formula (c1-1), it is preferred to be represented by the following general formula (c1-1-1).

[0191] [Chemistry 46]

[0192]

[0193] In the above general formula (c1-1-1), Q 11 and Q 12 Each group is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; to improve solvent solubility, at least one of these groups is preferably trifluoromethyl. m1 is an integer from 0 to 4, preferably 1. R fa1 The hydrocarbon group may contain heteroatoms and has 1 to 35 carbon atoms. Regarding the aforementioned heteroatoms, oxygen, nitrogen, sulfur, halogen atoms, etc., are preferred, with oxygen atoms being more preferred. Regarding the aforementioned hydrocarbon group, considering the high resolution that can be obtained when forming fine patterns, it is particularly preferred to have 6 to 30 carbon atoms.

[0194] In the above general formula (c1-1-1), R fa1 The hydrocarbon group represented by carbon number 1 to 35 can be saturated or unsaturated, and can be any of the following: straight chain, branched, or cyclic. Specific examples include alkyl groups with 1 to 35 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecanyl, and eicosyl; cyclic saturated hydrocarbon groups with 3 to 35 carbon atoms, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norcamphenyl, norcamphenylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups with 2 to 35 carbon atoms, such as allyl and 3-cyclohexenyl; aryl groups with 6 to 35 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, and 9-fluorenyl; aralkyl groups with 7 to 35 carbon atoms, such as benzyl and diphenylmethyl; and groups obtained by combining them.

[0195] Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, and halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, and nitrogen atoms. As a result, it may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulopentalide ring, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl, etc. Examples of hydrocarbon groups containing heteroatoms include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidemethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl.

[0196] In the above general formula (c1-1-1), L a1 The bonds can be single bonds, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. From a synthetic point of view, ether bonds or ester bonds are preferred, and ester bonds are even more preferred.

[0197] Regarding specific examples of anions represented by the above general formula (c1-1-1), the following examples can be listed, but are not limited to these. Furthermore, in the following formula, Q... 11 As mentioned above, Ac is an acetyl group.

[0198] [Chemistry 47]

[0199]

[0200] [Chemistry 48]

[0201]

[0202] [Chemistry 49]

[0203]

[0204] [Transformation 50]

[0205]

[0206] [Chemistry 51]

[0207]

[0208] [Chemistry 52]

[0209]

[0210] [Chemistry 53]

[0211]

[0212] [Chemistry 54]

[0213]

[0214] [Chemistry 55]

[0215]

[0216] [Chemistry 56]

[0217]

[0218] In the above general formula (c1-2), R fb1 and R fb2Each of the above-described hydrocarbon groups consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specifically, examples can be given of R as exemplified in the above general formula (c1-1-1). fa1 Those representing hydrocarbon groups are the same. Regarding R... fb1 and R fb2 Preferably, it is a straight-chain fluorinated alkyl group with fluorine atoms or 1 to 4 carbon atoms. Also, R fb1 and R fb2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-N). - -SO2-CF2-) together form a ring, in which case R fb1 and R fb2 For groups formed by mutual bonding, fluorinated ethylidene or fluorinated propylene is preferred.

[0219] In the above general formula (c1-3), R fc1 R fc2 and R fc3 Each of the above-described hydrocarbon groups consists independently of a fluorine atom or may contain heteroatoms and has 1 to 40 carbon atoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specifically, examples can be given of R as exemplified in the above general formula (c1-1-1). fa1 Those representing hydrocarbon groups are the same. Regarding R... fc1 R fc2 and R fc3 Preferably, it is a straight-chain fluorinated alkyl group with fluorine atoms or 1 to 4 carbon atoms. Also, R fc1 and R fc2 They can also bond to each other and to the groups they are bonded to (-CF2-SO2-C). - -SO2-CF2-) together form a ring, in which case R fc1 and R fc2 For groups formed by mutual bonding, fluorinated ethylidene or fluorinated propylene is preferred.

[0220] In the above general formula (c1-4), R fd It can be a hydrocarbon group with 1 to 40 carbon atoms, which may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specifically, examples can be given, such as R in the above general formula (c1-1-1), which has already been exemplified. fa1 Those representing hydrocarbon groups are the same.

[0221] Specific examples of anions represented by the above general formula (c1-4) can be listed below, but are not limited to these.

[0222] [Chemistry 57]

[0223]

[0224] [Chem.58]

[0225]

[0226] Regarding the aforementioned examples of non-nucleophilic relative ions, further examples can be given of anions having aromatic rings substituted with iodine or bromine atoms. Specific examples of such anions can be represented by the following general formulas (c1-5).

[0227] [Chemistry 59]

[0228]

[0229] In the above general formula (c1-5), x is an integer satisfying 1≤x≤3. y and z are integers satisfying 1≤y≤5, 0≤z≤3, and 1≤y+z≤5. y is preferably an integer satisfying 1≤y≤3, more preferably 2 or 3. z is preferably an integer satisfying 0≤z≤2.

[0230] In the above general formula (c1-5), X BI The atoms are either iodine or bromine, and when x and / or y are 2 or more, they can be the same or different.

[0231] In the above general formula (c1-5), L 11 It is a saturated hydrocarbon group with 1 to 6 carbon atoms, which can be a single bond, ether bond, ester bond, or may contain ether or ester bonds. The aforementioned saturated hydrocarbon group can be any of the following: straight-chain, branched, or cyclic.

[0232] In the above general formula (c1-5), L 12 When x is 1, it is a single bond or a divalent linker with 1 to 20 carbon atoms; when x is 2 or 3, it is a (x+1) valent linker with 1 to 20 carbon atoms. This linker may also contain oxygen, sulfur, or nitrogen atoms.

[0233] In the above general formula (c1-5), R fe The carbon groups are hydroxyl, carboxyl, fluorine, chlorine, bromine, amino, or may contain fluorine, chlorine, bromine, hydroxyl, amino, or ether bonds, and are hydrocarbon groups having 1 to 20 carbon atoms, hydrocarbon oxy groups having 1 to 20 carbon atoms, hydrocarbon carbonyl groups having 2 to 20 carbon atoms, hydrocarbon carbonyl oxy groups having 2 to 20 carbon atoms, or hydrocarbon sulfonyl oxy groups having 1 to 20 carbon atoms, or -N(R) groups. feA (R) feB ), -N(R feC )-C(=O)-R feD Or -N(R) feC)-C(=O)-OR feD R feA and R feB Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. R feC It is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms. R feD It is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may also contain a halogen atom, a hydroxyl group, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbon carbonyl oxy group having 2 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon group may be saturated or unsaturated, and may be any of straight-chain, branched, or cyclic. The aforementioned hydrocarbon group, hydrocarbon oxy group, hydrocarbon carbonyl group, hydrocarbon oxycarbonyl group, hydrocarbon carbonyl oxy group, and hydrocarbon sulfonyl oxy group may be any of straight-chain, branched, or cyclic. When x and / or z are 2 or more, each R fe They can be the same or different.

[0234] Among these, R fe Preferably, it is hydroxyl, -N(R) feC )-C(=O)-R feD -N(R) feC )-C(=O)-OR feD Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc.

[0235] In the above general formula (c1-5), Rf 11 ~Rf 14 Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of these is a fluorine atom or a trifluoromethyl group. Also, Rf 11 With Rf 12 They can also combine to form carbonyl groups. In particular, Rf 13 and Rf 14 All of them contain fluorine atoms, which is ideal.

[0236] Regarding specific examples of anions represented by the above general formula (c1-5), the following examples can be listed, but are not limited to these. Furthermore, in the following formula, X... BI Same as above.

[0237] [Transformation 60]

[0238]

[0239] [Chemistry 61]

[0240]

[0241] [Chemistry 62]

[0242]

[0243] [Chemistry 63]

[0244]

[0245] [Chemistry 64]

[0246]

[0247] [Chemistry 65]

[0248]

[0249] [Chemistry 66]

[0250]

[0251] [Chemistry 67]

[0252]

[0253] [Chemistry 68]

[0254]

[0255] [Chemistry 69]

[0256]

[0257] [Chemistry 70]

[0258]

[0259] [Chemistry 71]

[0260]

[0261] [Chemistry 72]

[0262]

[0263] [Chemistry 73]

[0264]

[0265] [Chemistry 74]

[0266]

[0267] [Chemistry 75]

[0268]

[0269] [Chemistry 76]

[0270]

[0271] [Chemistry 77]

[0272]

[0273] [Chemistry 78]

[0274]

[0275] [Chemistry 79]

[0276]

[0277] [Chemistry 80]

[0278]

[0279] [Chemistry 81]

[0280]

[0281] [Chemistry 82]

[0282]

[0283] Regarding the aforementioned non-nucleophilic relative ions, the following can also be used: fluorobenzenesulfonic acid anions bonded to aromatic groups containing iodine atoms as described in Japanese Patent No. 6648726; anions with a mechanism that decomposes by acid as described in International Publication No. 2021 / 200056 and Japanese Patent Application Publication No. 2021-070692; anions with cyclic ether groups as described in Japanese Patent Application Publication No. 2018-180525 and Japanese Patent Application Publication No. 2021-035935; and anions as described in Japanese Patent Application Publication No. 2018-092159.

[0284] Regarding the aforementioned non-nucleophilic relative ions, it is also possible to further use the bulky benzenesulfonic acid derivative anions without fluorine atoms described in Japanese Patent Application Publication No. 2006-276759, Japanese Patent Application Publication No. 2015-117200, Japanese Patent Application Publication No. 2016-065016, and Japanese Patent Application Publication No. 2019-202974, as well as the benzenesulfonic acid anions bonded to an aromatic group containing iodine atoms and without fluorine atoms, and the alkylsulfonic acid anions described in Japanese Patent No. 6645464.

[0285] Regarding the aforementioned non-nucleophilic relative ions, it is also possible to further use the anions of disulfonic acid described in Japanese Patent Application Publication No. 2015-206932, the anions of sulfonamide and sulfonylimide with one side being sulfonic acid and the other side being different, as described in International Patent Application Publication No. 2020 / 158366, and the anions of sulfonic acid and carboxylic acid with one side being sulfonic acid and the other side being different, as described in Japanese Patent Application Publication No. 2015-024989.

[0286] In the above general formulas (c2) and (c3), L 1 The bonds can be single bonds, ether bonds, ester bonds, carbonyl bonds, sulfonate bonds, carbonate bonds, or carbamate bonds. Among these, from a synthetic point of view, ether bonds, ester bonds, or carbonyl bonds are preferred, and ester bonds or carbonyl bonds are even more preferred.

[0287] In the above general formula (c2), Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf 1 and Rf 2 In order to increase the acid strength of the produced acid, fluorine atoms are ideal. Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf is used to improve solvent solubility. 3 and Rf 4 At least one of them is trifluoromethyl, which is more ideal.

[0288] In the above general formula (c3), Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. However, not all Rf groups are present. 5 and Rf 6 The case where both are hydrogen atoms. Among these, Rf... 5 and Rf 6 At least one of them is trifluoromethyl, which is more ideal.

[0289] In the above general formulas (c2) and (c3), d is an integer from 0 to 3, preferably 1.

[0290] Regarding specific examples of the anion in repeating unit c2, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A As mentioned above, Me is a methyl group.

[0291] [Chemistry 83]

[0292]

[0293] [Chemistry 84]

[0294]

[0295] [Chemistry 85]

[0296]

[0297] [Chemistry 86]

[0298]

[0299] [Chemistry 87]

[0300]

[0301] [Chemistry 88]

[0302]

[0303] [Chemistry 89]

[0304]

[0305] [Chemistry 90]

[0306]

[0307] [Chemistry 91]

[0308]

[0309] Regarding specific examples of the anion in repeating unit c3, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[0310] [Chemistry 92]

[0311]

[0312] [Chemistry 93]

[0313]

[0314] [Chemistry 94]

[0315]

[0316] [Chemistry 95]

[0317]

[0318] [Chemistry 96]

[0319]

[0320] [Chemistry 97]

[0321]

[0322] [Chem. 98]

[0323]

[0324] [Chemistry 99]

[0325]

[0326] Regarding specific examples of the anion in repeating unit c4, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A Same as above.

[0327] [Chemistry 100]

[0328]

[0329] In the above general formulas (c2) to (c4), A + The cation is an onium cation. Among the aforementioned onium cations, ammonium cations, sulfonium cations, and monium cations can be listed, with sulfonium cations and monium cations being preferred. Among the aforementioned onium cations, sulfonium cations represented by the following general formula (cation-1) or monium cations represented by the following general formula (cation-2) are preferred.

[0330] [Chemistry 101]

[0331]

[0332] In the above general formulas (cation-1) and (cation-2), R ct1 ~R ct5 Each is an independent hydrocarbon group consisting of halogen atoms or may contain heteroatoms, and has 1 to 30 carbon atoms.

[0333] Regarding R ct1 ~R ct5 Examples of halogen atoms that can be represented include fluorine, chlorine, bromine, and iodine atoms.

[0334] R ct1 ~R ct5The hydrocarbon group representing 1 to 30 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornel, and adamantyl; alkenyl groups with 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups with 3 to 30 carbon atoms such as cyclohexenyl; aryl groups with 6 to 30 carbon atoms such as phenyl, naphthyl, and thiophene; aralkyl groups with 7 to 30 carbon atoms such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these, preferably aryl. Furthermore, a portion of the hydrogen atom in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon group can be replaced by a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the hydrocarbon group may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, nitro, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonate ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.

[0335] Also, R ct1 and R ct2 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. In this case, the structure of the aforementioned rings can be represented by the following formulas, etc.

[0336] [Chemistry 102]

[0337]

[0338] (In the formula, the dashed line represents the intersection with R) ct3 (Atomic bonds.)

[0339] Specific examples of sulfonium cations represented by the above general formula (cation-1) can be listed below, but are not limited to these.

[0340] [Chemistry 103]

[0341]

[0342] [Chemistry 104]

[0343]

[0344] [Chemistry 105]

[0345]

[0346] [Chemistry 106]

[0347]

[0348] [Chemistry 107]

[0349]

[0350] [Chemistry 108]

[0351]

[0352] [Chemistry 109]

[0353]

[0354] [Chemical 110]

[0355]

[0356] [Chemistry 111]

[0357]

[0358] [Chemistry 112]

[0359]

[0360] [Chemistry 113]

[0361]

[0362] [Chemistry 114]

[0363]

[0364] [Chemistry 115]

[0365]

[0366] [Chemistry 116]

[0367]

[0368] [Chemistry 117]

[0369]

[0370] [Chemistry 118]

[0371]

[0372] [Chemistry 119]

[0373]

[0374] [Chemistry 120]

[0375]

[0376] [Chemistry 121]

[0377]

[0378] [Chemistry 122]

[0379]

[0380] [Chemistry 123]

[0381]

[0382] [Chemistry 124]

[0383]

[0384] [Chemistry 125]

[0385]

[0386] [Chemistry 126]

[0387]

[0388] [Chemistry 127]

[0389]

[0390] [Chemistry 128]

[0391]

[0392] [Chemistry 129]

[0393]

[0394] Specific examples of citriium cations represented by the above general formula (cation-2) can be listed below, but are not limited to these.

[0395] [Chemistry 130]

[0396]

[0397] [Chemistry 131]

[0398]

[0399] Regarding the specific structure of the repeating units c1 to c4, any combination of the aforementioned anions and cations can be listed.

[0400] Among the repeating units c1 to c4, from the perspective of controlling acid diffusion, repeating units c2, c3, and c4 are preferred; from the perspective of the acid strength of the generated acid, repeating units c2 and c4 are even more preferred; and from the perspective of solvent solubility, repeating unit c2 is even more preferred.

[0401] The aforementioned polymeric compounds may also contain repeating units represented by the following general formula (a1) (hereinafter also referred to as repeating unit a1).

[0402] [Chemistry 132]

[0403]

[0404] In the above general formula (a1), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0405] In the above general formula (a1), X 11 It is a single bond, phenylene, naphthylene, or *-C(=O)-OX 111 - The aforementioned phenylene or naphthylene group may also be substituted by an alkoxy or halogen atom with 1 to 10 carbon atoms, which may also contain a fluorine atom. X 111 It is a saturated alkylene group, phenylene group, or naphthylene group having 1 to 10 carbon atoms. The aforementioned saturated alkylene group may also contain hydroxyl groups, ether bonds, ester bonds, or lactone rings. * indicates an atomic bond with a carbon atom in the main chain.

[0406] In the above general formula (a1), AL 11 It is an acid-indestructible group. For example, those described in Japanese Patent Application Publication No. 2013-080033 and Japanese Patent Application Publication No. 2013-083821 are examples of acid-indestructible groups.

[0407] Generally speaking, for the aforementioned acid-instable groups, those represented by the following general formulas (AL-11) to (AL-13) can be listed.

[0408] [Chemistry 133]

[0409]

[0410] (In the formula, the dashed lines represent atomic bonds.)

[0411] In the above general formulas (AL-11) and (AL-12), R L11 and R L12 Each hydrocarbon group is independently composed of 1 to 40 carbon atoms and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Preferably, the hydrocarbon groups have 1 to 20 carbon atoms.

[0412] In the above general formula (AL-11), k is an integer from 0 to 10, preferably an integer from 1 to 5.

[0413] In the above general formula (AL-12), R L13 and R L14 Each group is independently composed of a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups can be saturated or unsaturated, and can be linear, branched, or cyclic. Of the aforementioned hydrocarbon groups, those having 1 to 20 carbon atoms are preferred. Furthermore, R... L12 R L13 and R L14 Any two of them can also bond to each other and together with the carbon atoms they are bonded to, or carbon atoms and oxygen atoms, to form a ring with 3 to 20 carbon atoms. Of the aforementioned rings, a ring with 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0414] In the above general formula (AL-13), R L15 R L16 and R L17 Each group is an independent hydrocarbon group having 1 to 20 carbon atoms, and may also contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The aforementioned hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Of the aforementioned hydrocarbon groups, those having 1 to 20 carbon atoms are preferred. Furthermore, R... L15 R L16 and R L17 Any two of them can also bond to each other and together with the carbon atoms they are bonded to form a ring with 3 to 20 carbon atoms. Of the aforementioned rings, a ring with 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0415] Regarding specific examples of the repeating unit a1, the following can be listed, but are not limited to these. Furthermore, in the following formula, R... A and AL 11 Same as above.

[0416] [Chemistry 134]

[0417]

[0418] [Chemistry 135]

[0419]

[0420] [Chemistry 136]

[0421]

[0422] The aforementioned polymeric compounds may also contain repeating units represented by the following general formula (a2) (hereinafter also referred to as repeating unit a2).

[0423] [Chemistry 137]

[0424]

[0425] In the above general formula (a2), R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 22 It represents a single bond or *-C(=O)-O-. * indicates an atomic bond with a carbon atom in the main chain. R 111 It can be a halogen atom, a cyano group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms; a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms; or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms. AL 22 This is an acid-labile group. Regarding the aforementioned acid-labile groups, examples such as AL can be listed and exemplified. 11 The same type of unstable acid group is represented. a is an integer from 0 to 4, preferably 0 or 1.

[0426] Regarding specific examples of the repeating unit a2, the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R... A and AL 22 Same as above.

[0427] [Chemistry 138]

[0428]

[0429] [Chemistry 139]

[0430]

[0431] The aforementioned polymeric compounds may also contain repeating units (hereinafter also referred to as repeating units d) with structures having hydroxyl groups protected by acid-indestructible groups. As for repeating units d, there is no particular limitation if they have a structure with one or more hydroxyl groups protected, and the protecting groups are decomposed by the action of acid to generate hydroxyl groups, but they are preferably represented by the following general formula (d1).

[0432] [Chemistry 140]

[0433]

[0434] In the above general formula (d1), R A Same as above. R 41 It can also contain heteroatoms and is a (e+1) valence hydrocarbon group with 1 to 30 carbon atoms. R 42 It is an acid-labile group. e is an integer from 1 to 4.

[0435] In the above general formula (d1), R 42 The acid-labile group represented may be one that is deprotected by the action of an acid to generate a hydroxyl group. The structure of R 42 is not particularly limited. Preferably, it is an acetal structure, a ketal structure, an alkoxycarbonyl group, an alkoxymethyl group represented by the following general formula (d2), etc. Particularly preferably, it is an alkoxymethyl group represented by the following general formula (d2).

[0436] [Chemical formula 141]

[0437]

[0438] (In the formula, * represents an atomic bond. R 43 is a hydrocarbon group having 1 to 15 carbon atoms.)

[0439] Regarding the acid-labile group represented by R 42 , the alkoxymethyl group represented by the above general formula (d2), and specific examples of the repeating unit d, the same ones as those exemplified in the description of the repeating unit d described in Japanese Patent Laid-Open No. 2020-111564 can be cited. <OOO1511>The aforementioned polymer compound may also contain a repeating unit e derived from indene, benzofuran, benzothiophene, acenaphthene, chromone, coumarin, norbornadiene, or their derivatives. Regarding specific examples of the monomer that imparts the repeating unit e, the following can be cited, but are not limited to these.

[0441] [Chemical formula 142]

[0442]

[0443] The aforementioned polymer compound may also contain a repeating unit f derived from indan, vinylpyridine, or vinylcarbazole.

[0444] In the polymer compound of the present invention, the content ratios of the repeating units A, a1, a2, b1, b2, c1 to c4, d, e, and f are preferably 0 < A ≤ 0.8, 0 ≤ a1 ≤ 0.8, 0 ≤ a2 ≤ 0.8, 0 ≤ bI ≤ 0.6, 0 ≤ b2 ≤ 0.6, 0 ≤ c1 ≤ 0.4, 0 ≤ c2 ≤ 0.4, 0 ≤ c3 ≤ 0.4, 0 ≤ c4 ≤ 0.4, 0 ≤ d ≤ 0.5, 0 ≤ e ≤ 0.3, and 0 ≤ f ≤ 0.3, more preferably 0 < A ≤ 0.5, 0 ≤ a1 ≤ 0.5, 0 ≤ a2 ≤ 0.5, 0 ≤ b1 ≤ 0.5, 0 ≤ bI ≤ 0.5, 0 ≤ c1 ≤ 0.3, 0 ≤ c2 ≤ 0.3, 0 ≤ c3 ≤ 0.3, 0 ≤ c4 ≤ 0.3, 0 ≤ d ≤ 0.3, 0 ≤ e ≤ 0.3, and 0 ≤ f ≤ 0.3. However, A + a1 + a2 + b1 + b2 + c1 + c2 + c3 + c4 + d + e + f = 1.

[0445] The weight-average molecular weight (Mw) of the aforementioned polymer compound is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. If Mw is within this range, sufficient etch resistance can be obtained, and there is no possibility of a decrease in resolution due to the difference in dissolution rates before and after exposure. Furthermore, in this invention, Mw is a converted value of polystyrene obtained using gel permeation chromatography (GPC) with THF or N,N-dimethylformamide (DMF) as a solvent.

[0446] Furthermore, the molecular weight distribution (Mw / Mn) of the aforementioned polymer compounds tends to increase with the refinement of the pattern regularity. Therefore, in order to obtain a chemically amplified resist composition that can be ideally used for fine pattern sizes, a narrow dispersion of Mw / Mn of 1.0 to 2.0 is preferred. If it is within this range, there are fewer polymers with lower or higher Mw molecular weights, and there is no possibility of foreign matter being observed on the pattern after exposure, or deterioration of the pattern shape.

[0447] To synthesize the aforementioned polymeric compounds, for example, polymerization can be carried out by adding a free radical polymerization initiator to the monomer that will impart the aforementioned repeating units in an organic solvent and heating it.

[0448] Examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these polymerization initiators added relative to the total monomers being polymerized is preferably 0.01–25 mol%. The reaction temperature is preferably 50–150°C, more preferably 60–100°C. The reaction time is preferably 2–24 hours, and from a production efficiency perspective, 2–12 hours is more preferably.

[0449] The aforementioned polymerization initiator can be added to the aforementioned monomer solution and supplied to the reactor, or the polymerization initiator solution can be prepared separately from the monomer solution and each solution can be supplied to the reactor independently. Because there is a possibility that polymerization may proceed during the waiting time due to free radicals generated from the polymerization initiator, resulting in the formation of ultrapolymers, it is ideal, from a quality control perspective, to prepare and add the monomer solution and polymerization initiator solution independently. Acid-labile groups can be used directly introduced into the monomer, or they can be protected or partially protected after polymerization. Furthermore, for molecular weight adjustment, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used concurrently. In this case, the amount of these chain transfer agents added relative to the total amount of monomers polymerized is preferably 0.01 to 20 mol%.

[0450] In the case of monomers containing hydroxyl groups, the hydroxyl groups can be replaced with acetal groups such as ethoxy-ethoxy, which are easily deprotected by acids, during polymerization, and then deprotected by weak acids and water after polymerization. Alternatively, they can be replaced with acetyl, formyl, neopentyl, etc., and then subjected to alkaline hydrolysis after polymerization.

[0451] In the case of copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, a free radical polymerization initiator can be added to hydroxystyrene or hydroxyvinylnaphthalene and other monomers in an organic solvent and the polymerization can be carried out by heating. Alternatively, acetoxystyrene or acetoxyvinylnaphthalene can be used and the acetoxy group can be deprotected by alkaline hydrolysis after polymerization to produce polyhydroxystyrene or hydroxyvinylnaphthalene.

[0452] For the alkali used in alkaline hydrolysis, ammonia, triethylamine, etc., can be used. Furthermore, the preferred reaction temperature is -20 to 100°C, more preferably 0 to 60°C. The preferred reaction time is 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0453] Furthermore, the amount of each monomer in the aforementioned monomer solution can be appropriately set, for example, in a manner that creates an ideal content ratio for the aforementioned repeating units.

[0454] The polymer obtained in the aforementioned manufacturing method can be used to make the final product from the reaction solution obtained by the polymerization reaction, or the powder obtained by the refining steps such as adding the reaction solution to a poor solvent to obtain the powder can be used as the final product. Considering the viewpoints of work efficiency and quality stabilization, it is more ideal to use the polymer solution obtained by dissolving the powder obtained by the refining step into the solvent as the final product.

[0455] For specific examples of solvents used at this time, examples include ketones such as cyclohexanone and methyl-2-n-pentyl ketone as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; and propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol dimethyl ether. Ethers such as diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; alcohols such as diacetone alcohol (DAA); high-boiling-point alcohol solvents such as diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, and 1,3-butanediol; and their mixed solvents.

[0456] In the aforementioned polymer solution, the polymer concentration is preferably 0.01–30% by mass, more preferably 0.1–20% by mass.

[0457] Filtration of the aforementioned reaction solution and polymer solution using a filter is ideal. By using a filter, foreign matter and gel that can cause defects can be removed, which is effective in stabilizing the quality.

[0458] Regarding the materials used in the aforementioned filter filtration, examples include fluorocarbon-based, cellulose-based, nylon-based, polyester-based, and hydrocarbon-based materials. In the filtration step involving the resist composition, filters made of fluorocarbons such as Teflon (a registered trademark), hydrocarbons such as polyethylene or polypropylene, or nylon are preferred. The pore size of the filter can be appropriately selected to match the target cleanliness level, preferably below 100 nm, and more preferably below 20 nm. Furthermore, a single filter can be used, or multiple filters can be used in combination. The filtration method can also involve passing the solution only once, but multiple filtrations through solution circulation are more ideal. The filtration step can be performed in any order and number of times during the polymer manufacturing process; preferably, the reaction solution after polymerization, the polymer solution, or both are filtered.

[0459] (A) A single base resin may be used alone, or two or more resins with different composition ratios, Mw and / or Mw / Mn ratios may be used in combination. Furthermore, (A) in addition to the aforementioned polymeric compounds, the base resin may also contain hydrides of ring-opening metathesis polymers. Regarding these hydrides of ring-opening metathesis polymers, those described in Japanese Patent Application Publication No. 2003-066612 may be used.

[0460] [(B) Organic solvents]

[0461] The chemically amplified resist composition of the present invention contains an organic solvent as component (B). There is no particular limitation as to the organic solvent (B), which is capable of dissolving the aforementioned components and the components described below. Examples of such organic solvents include ketones such as cyclopentanone, cyclohexanone, and methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ketols such as DAA; ethers such as PGME, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as GBL; and mixed solvents thereof.

[0462] Among these (B) organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, DAA, and mixtures thereof are preferred as having particularly excellent solubility in the base resin of component (A).

[0463] In the chemically amplified resist composition of the present invention, the content of (B) organic solvent is preferably 200 to 5,000 parts by weight, and more preferably 400 to 3,500 parts by weight, relative to 80 parts by weight of (A) base resin. (B) Organic solvent may be used alone or in combination of two or more.

[0464] [(C) Quenching agent]

[0465] The chemically amplified resist composition of the present invention may also contain a quencher as component (C). Furthermore, in the present invention, the quencher refers to a material that prevents the diffusion of acid generated from the photoacid generator in the chemically amplified resist composition to the unexposed area by capturing the acid, and is used to form a desired pattern.

[0466] Regarding (C) quenchers, examples of onium salts represented by the following general formulas (2) or (3) can be listed.

[0467] [Chemistry 143]

[0468]

[0469] In the above general formula (2), R q1 It is a hydrocarbon group with 1 to 40 carbon atoms, which may contain hydrogen atoms or heteroatoms, but excludes the case where the hydrogen atom at the α-position of the sulfonic acid group is replaced by a fluorine atom or a fluoroalkyl group. In the above general formula (3), R q2 Hydrocarbon groups consisting of 1 to 40 carbon atoms, which may also contain heteroatoms.

[0470] R q1The hydrocarbon groups representing 1 to 40 carbon atoms can specifically include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and other alkyl groups with 1 to 40 carbon atoms; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norcamphenyl, tricyclic [5.2.1.0] 2,6 [Cyclic saturated hydrocarbon groups with 3 to 40 carbon atoms, such as decyl and adamantyl; aryl groups with 6 to 40 carbon atoms, such as phenyl, naphthyl, and anthracene. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned hydrocarbon groups may be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, these groups may contain hydroxyl, fluorine, chlorine, bromine, iodine, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone ring, sulfonyl lactone ring, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups.]

[0471] R q2 The hydrocarbon group represented, in particular, is not limited to the example already shown as R. q1 In addition to the specific examples of substituents, examples may also include fluorinated saturated hydrocarbon groups such as trifluoromethyl and trifluoroethyl, fluorinated aryl groups such as pentafluorophenyl and 4-trifluoromethylphenyl.

[0472] Specific examples of onion salt anions represented by the above general formula (2) can be listed below, but are not limited to these.

[0473] [Chemistry 144]

[0474]

[0475] [Chemistry 145]

[0476]

[0477] [Chemistry 146]

[0478]

[0479] [Chemistry 147]

[0480]

[0481] Specific examples of onion salt anions represented by the above general formula (3) can be listed below, but are not limited to these.

[0482] [Chemistry 148]

[0483]

[0484] [Chemistry 149]

[0485]

[0486] [Chemistry 150]

[0487]

[0488] In the above general formulas (2) and (3), Mq + The cation is an onium cation. Among the aforementioned onium cations, it is preferred to be a sulfonium cation represented by the above general formula (cation-1), a monium cation represented by the above general formula (cation-2), or an ammonium cation represented by the following general formula (cation-3).

[0489] [Chemistry 151]

[0490]

[0491] In the above general formula (cation-3), R ct6 ~R ct9 Each can be an independent hydrocarbon group with 1 to 40 carbon atoms, and may also contain heteroatoms. Also, R ct6 With R ct7 They can also bond to each other and form rings together with the nitrogen atoms to which they are bonded. Regarding the aforementioned hydrocarbon groups, examples exemplified in the descriptions of the above general formulas (cation-1) and (cation-2) as R can be listed. ct1 ~R ct5 The same applies to hydrocarbon groups.

[0492] Specific examples of ammonium cations represented by the above general formula (cation-3) can be listed below, but are not limited to these.

[0493] [Chemistry 152]

[0494]

[0495] Regarding specific examples of onium salts represented by the above general formula (2) or (3), any combination of the aforementioned anions and cations can be listed. Furthermore, these onium salts can be easily prepared using ion exchange reactions employing known organic chemical methods. For information on ion exchange reactions, please refer to, for example, Japanese Patent Application Publication No. 2007-145797.

[0496] The onium salts represented by the above general formula (2) or (3) function as quenchers in the chemically amplified resist composition of the present invention. This is because the relative anions of the aforementioned onium salts are conjugate bases of weak acids. The term "weak acid" here refers to an acidity that indicates an inability to deprotect the acid-instable groups of the units containing acid-instable groups used in the base resin (A). The onium salts represented by the above general formula (2) or (3) function as quenchers when used in combination with a conjugate base having a strong acid, such as sulfonic acid with fluorinated α-position, as an onium salt-type photoacid generator with a relative anion. In other words, when onium salts that produce strong acids like α-fluorinated sulfonic acid are mixed with onium salts that produce weak acids like unfluorinated sulfonic acid and carboxylic acid, the strong acid generated from the photoacid generator by high-energy radiation collides with the onium salt containing unreacted weak acid anions. This results in the release of the weak acid through salt exchange, generating an onium salt containing strong acid anions. During this process, the strong acid is exchanged with the weak acid, which has a lower catalyst energy, thus seemingly deactivating the acid and allowing for controlled acid diffusion.

[0497] Furthermore, regarding the quencher (C), the onium salt having a sulfonium cation and a benzene oxide anion site within the same molecule as described in Japanese Patent No. 6848776 can also be used. In addition, the onium salt having a sulfonium cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6583136, Japanese Patent Application Publication No. 2020-200311, and the onium salt having a monazine cation and a carboxylate anion site within the same molecule as described in Japanese Patent No. 6274755 can also be used.

[0498] Here, when the photoacid generator producing the strong acid is an onium salt, it is believed that, as mentioned above, the strong acid generated by high-energy ray irradiation can be exchanged for a weak acid. However, on the other hand, the weak acid generated by high-energy ray irradiation is unlikely to collide with the onium salt that produces the unreacted strong acid to undergo salt exchange. This is because onium cations more readily form ion pairs with the anions of strong acids.

[0499] When the chemically amplified resist composition of the present invention contains an onium salt represented by the above general formula (2) or (3) as a quencher in (C), its content is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 80 parts by mass of the base resin in (A). If the onium salt type quencher in component (C) is within the aforementioned range, then good resolution and no significant reduction in sensitivity are desirable. The onium salt represented by the above general formula (2) or (3) can be used alone or in combination of two or more.

[0500] The chemically amplified resist composition of the present invention may also contain a nitrogen-containing compound as a (C) quencher. Regarding the nitrogen-containing compound of component (C), primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103 can be cited, particularly amine compounds having hydroxyl groups, ether bonds, ester bonds, lactone rings, cyano groups, or sulfonate bonds. Furthermore, compounds obtained by protecting primary or secondary amines with urethane groups, as described in Japanese Patent No. 3790649, can also be cited.

[0501] Furthermore, regarding nitrogen-containing compounds, sulfonate sulfonates with nitrogen-containing substituents can also be used. Such compounds function as quenchers in unexposed areas, but as photodegrading bases in exposed areas, losing their quenching ability due to neutralization with their own generating acid. By using photodegrading bases, the contrast between exposed and unexposed areas can be further enhanced. For examples of photodegrading bases, see, for instance, Japanese Patent Application Laid-Open No. 2009-109595 and Japanese Patent Application Laid-Open No. 2012-046501.

[0502] When the chemically amplified resist composition of the present invention contains a nitrogen-containing compound as (C) quencher, its content, relative to 80 parts by weight of (A) base resin, is preferably 0.001 to 12 parts by weight, more preferably 0.01 to 8 parts by weight. The aforementioned nitrogen-containing compound may be used alone or in combination of two or more.

[0503] [(D) Photoacid generator]

[0504] The chemically amplified resist composition of the present invention may also contain a photoacid generator other than the photoacid generator bonded to the polymer backbone of component (A) as component (D). There are no particular limitations on other photoacid generators, as they are compounds that generate acid upon irradiation by high-energy rays. Ideal other photoacid generators may be represented by the following general formulas (4) or (5).

[0505] [Chemistry 153]

[0506]

[0507] In the above general formulas (4) and (5), R 101 ~R 105 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, and may also contain heteroatoms. Also, R 101 R 102 and R 103Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to. Regarding the aforementioned hydrocarbon groups, examples of those exemplified in the description of the above general formulas (cation-1) and (cation-2) as R can be listed. ct1 ~R ct5 Those representing hydrocarbon groups are the same.

[0508] Regarding specific examples of sulfonium salt cations represented by the above general formula (4), those identical to those already exemplified as sulfonium cations represented by the above general formula (cation-1) can be listed. Regarding specific examples of zirconia salt cations represented by the above general formula (5), those identical to those already exemplified as zirconia cations represented by the above general formula (cation-2) can be listed.

[0509] In the above general formulas (4) and (5), Xa - It is an anion of a strong acid. Regarding the anions of the aforementioned strong acids, any one of the general formulas (c1-1) to (c1-5) can be listed as an example.

[0510] Furthermore, other photoacid generators of component (D) are preferably represented by the following general formula (6).

[0511] [Chemistry 154]

[0512]

[0513] In the above general formula (6), R 201 and R 202 Each can be an independent hydrocarbon group with 1 to 30 carbon atoms, and may also contain heteroatoms. R 203 It can also contain a hydrocarbon group with 1 to 30 carbon atoms, which may also contain heteroatoms. Also, R 201 R 202 and R 203 Any two of them can also bond to each other and form a ring together with the sulfur atoms they are bonded to.

[0514] R 201 and R 202 The hydrocarbon group representing 1 to 30 carbon atoms can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornel, oxanorbornel, and tricyclic [5.2.1.0]. 2,6] Decyl, adamantyl, and other cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms; phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, anthracene, and other aryl groups with 6 to 30 carbon atoms; groups obtained by combining them, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. A portion of the -CH2- group in the aforementioned hydrocarbon group can also be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may also contain hydroxyl groups, cyano groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulcinolone rings, carboxylic anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0515] R 203 The alkylene groups representing carbon atoms from 1 to 30 can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane. -1,17-diyl and other alkyl diyl groups with 1 to 30 carbon atoms; cyclopentane diyl, cyclohexane diyl, norbornane diyl, adamantane diyl and other cyclic saturated hydrocarbon groups with 3 to 30 carbon atoms; phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, tert-butylnaphthylene and other aryl groups, etc. Furthermore, some or all of the hydrogen atoms in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Similarly, a portion of the -CH2- group in the aforementioned alkylene group can be replaced by groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms. As a result, the group may contain hydroxyl, cyano, fluorine, chlorine, bromine, iodine, carbonyl, ether, ester, sulfonate, carbonate, lactone, sulfonate, carboxylic anhydride (-C(=O)-OC(=O)-), or haloalkyl groups. Regarding the aforementioned heteroatoms, oxygen atoms are preferred.

[0516] In the above general formula (6), L A It is a hydrocarbon group with 1 to 20 carbon atoms, which may be a single bond, an ether bond, or may contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. For specific examples, those already exemplified as R can be listed. 203 Those representing alkylene groups with the same number of carbons from 1 to 20.

[0517] In the above general formula (6), X a X b X c and X d Each can be independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom. However, X a X b X c and X d At least one of them is a fluorine atom or a trifluoromethyl group.

[0518] Of the photoacid generators represented by the above general formula (6), those represented by the following general formula (6') are preferred.

[0519] [Chemistry 155]

[0520]

[0521] In the above general formula (6'), L A Same as above. X e It can be a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. R 301 R 302 and R 303 Each of the above-mentioned hydrocarbon groups consists independently of hydrogen atoms, or may contain heteroatoms, and has 1 to 20 carbon atoms. These hydrocarbon groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specifically, examples can be given, such as R in the general formula (c1-1-1) already illustrated. fa1 The hydrocarbon groups are the same. p and q are each independent integers from 0 to 5, and r is an integer from 0 to 4.

[0522] Regarding the photoacid generating agent represented by the above general formula (6), examples can be listed that are the same as those represented by formula (2) as exemplified in Japanese Patent Application Publication No. 2017-026980.

[0523] Among the aforementioned other photoacid generators, those containing anions represented by the above general formula (c1-1-1) or (c1-4) exhibit low acid diffusion and excellent solvent solubility, making them particularly desirable. Furthermore, those represented by the above general formula (6') exhibit extremely low acid diffusion, making them particularly desirable.

[0524] When the chemically amplified resist composition of the present invention contains a photoacid generator (D), its content, relative to 80 parts by weight of the base resin (A), is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 20 parts by weight. If the amount of photoacid generator (D) added is within the aforementioned range, the resolution is good, and there is no possibility of foreign matter being generated after development or during peeling of the resist film, which is ideal. One type of photoacid generator (D) can be used alone, or two or more can be used in combination.

[0525] [(E) Surfactant]

[0526] The chemically amplified resist composition of the present invention may also contain a surfactant as component (E). Regarding the surfactant (E), it is preferably a surfactant that is insoluble or poorly soluble in water but soluble in alkaline developing solution, or a surfactant that is insoluble or poorly soluble in both water and alkaline developing solution. For such surfactants, reference can be made to those described in Japanese Patent Application Publication Nos. 2010-215608 and 2011-016746.

[0527] Regarding surfactants that are insoluble or poorly soluble in water and alkaline developing solutions, among the surfactants described in the aforementioned publication, preferred ones are FC-4430 (manufactured by 3M Corporation), Surflon (registered trademark) S-381 (manufactured by AGC SEIMI CHEMICAL), OLFINE (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC SEIMI CHEMICAL), and oxane ring-opening polymers represented by the following general formula (surf-1).

[0528] [Chemistry 156]

[0529]

[0530] Here, R, Rf, A, B, C, m, and n, regardless of the foregoing description, apply only to the above general formula (surf-1). R is an aliphatic group with 2 to 5 carbon atoms, ranging from 2 to 4 valent. Regarding the aforementioned aliphatic groups, examples of 2-valent groups include ethylene, 1,4-butylene, 1,2-propylene, 2,2-dimethyl-1,3-propylene, and 1,5-pentane, while examples of 3- or 4-valent groups include the following.

[0531] [Chemistry 157]

[0532]

[0533] (In the formula, the dashed lines represent atomic bonds, which are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentyl tetrol, respectively.)

[0534] Among these, 1,4-butylene, 2,2-dimethyl-1,3-propylene, etc. are preferred.

[0535] Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. m is an integer from 0 to 3, n is an integer from 1 to 4, the sum of n and m is the valence of R, and is an integer from 2 to 4. A is 1. B is an integer from 2 to 25, preferably an integer from 4 to 20. C is an integer from 0 to 10, preferably 0 or 1. Furthermore, the arrangement of the constituent units in the above general formula (surf-1) is not specified; they can be block-bonded or randomly bonded. For details on the manufacture of surfactants based on partially fluorinated oxyheterocyclic butane ring-opening polymer systems, please refer to the specification of US Patent No. 5,650,483, etc.

[0536] Surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solutions are useful in ArF immersion lithography when no resist film is used. They reduce water penetration and leaching by aligning with the surface of the resist film. Therefore, they are useful for inhibiting the leaching of water-soluble components from the resist film and reducing damage to the exposure equipment. Furthermore, they are useful for dissolving in alkaline solutions after exposure or post-exposure baking (PEB) and are less likely to become foreign matter that could cause defects. Such surfactants, which are insoluble or sparingly soluble in water but soluble in alkaline developing solutions, are polymeric surfactants, also known as hydrophobic resins, and are particularly preferred for their high water repellency and improved hydrophobicity.

[0537] In particular, examples of such polymeric surfactants include those containing at least one repeating unit selected from any of the following general formulas (7A) to (7E).

[0538] [Chemistry 158]

[0539]

[0540] In the above general formulas (7A) to (7E), R B It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. W 1 It can be -CH2-, -CH2CH2-, -O-, or two separate -H groups. R s1 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R s2 It is a single bond, or a straight-chain or branched hydrocarbon group with 1 to 5 carbon atoms. R s3 Each is independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group, or an acid-labile group. In R s3 In the case of a hydrocarbon group or a fluorinated hydrocarbon group, an ether bond or a carbonyl group can also be inserted between the carbon-carbon bonds. s4 It is a (u+1) valence hydrocarbon group or a fluorinated hydrocarbon group with 1 to 20 carbon atoms. u is an integer from 1 to 3. s5Each is independently a hydrogen atom or -C(=O)-OR sa The group indicated by R. sa It is a fluorinated hydrocarbon group with 1 to 20 carbon atoms. R s6 It is a hydrocarbon group or a fluorinated hydrocarbon group with 1 to 15 carbon atoms, and an ether bond or a carbonyl group may also be inserted between its carbon-carbon bonds.

[0541] R s1 The hydrocarbon group representing 1 to 10 carbon atoms is preferably a saturated hydrocarbon group, and can be linear, branched, or cyclic. Specific examples include alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; and cyclic saturated hydrocarbon groups with 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, and norbornel. Among these, those with 1 to 6 carbon atoms are preferred.

[0542] R s2 The represented hydrocarbon group is preferably a saturated hydrocarbon group, and can be linear, branched, or cyclic. Specific examples include methylene, ethylene, propylene, butylene, and pentylene.

[0543] R s3 Or R s6 The hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include aliphatic unsaturated hydrocarbon groups such as saturated hydrocarbon groups, alkenyl groups, and alkynyl groups, with saturated hydrocarbon groups being preferred. Regarding the aforementioned saturated hydrocarbon groups, besides those already exemplified as R... s1 Besides those representing hydrocarbon groups, other examples include undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. Regarding R... s3 Or R s6 Regarding the fluorinated hydrocarbon group, examples include groups in which some or all of the hydrogen atoms of the carbon atoms bonded to the aforementioned hydrocarbon group are replaced by fluorine atoms. As mentioned above, ether bonds or carbonyl groups can also be inserted between these carbon-carbon bonds.

[0544] Regarding R s3 Specific examples of the acid-instable groups can be exemplified by groups represented by the above general formulas (AL-1) to (AL-3), trialkylsilyl groups with alkyl groups having 1 to 6 carbon atoms, and alkyl groups containing oxygen groups having 4 to 20 carbon atoms.

[0545] R s4 The (u+1) valence hydrocarbon group or fluorinated hydrocarbon group can be any of the following: straight chain, branched, or cyclic. In specific examples, groups obtained by further removing u hydrogen atoms from the aforementioned hydrocarbon group or fluorinated hydrocarbon group can be listed.

[0546] Rsa The fluorinated hydrocarbon group indicated is preferably saturated and can be any of the following: straight-chain, branched, or cyclic. Specific examples include those in which some or all of the hydrogen atoms of the aforementioned hydrocarbon groups are replaced by fluorine atoms. Specific examples include trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoro-1-propyl, 3,3,3-trifluoro-2-propyl, 2,2,3,3-tetrafluoropropyl, 1,1,1,3,3,3-hexafluoroisopropyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2,2,3,3,4,4,5,5,6,6,7,7-dodecylheptyl, 2-(perfluorobutyl)ethyl, 2-(perfluorohexyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, etc.

[0547] For specific examples of the repeating unit represented by any of the above general formulas (7A) to (7E), the following examples can be listed, but are not limited to these. Furthermore, in the following formula, R B Same as above.

[0548] [Chemistry 159]

[0549]

[0550] [Chemistry 160]

[0551]

[0552] [Chemistry 161]

[0553]

[0554] [Chemistry 162]

[0555]

[0556] [Chemistry 163]

[0557]

[0558] [Chemistry 164]

[0559]

[0560] The aforementioned polymeric surfactants may also contain other repeating units besides those represented by the general formulas (7A) to (7E). Examples of other repeating units include repeating units derived from methacrylic acid, α-trifluoromethacrylic acid derivatives, etc. In the aforementioned polymeric surfactants, it is preferable that the content of the repeating units represented by the general formulas (7A) to (7E) is 20 mol% or more of all repeating units, more preferably 60 mol% or more, and even more preferably 100 mol%.

[0561] The Mw of the aforementioned polymeric surfactant is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. The Mw / Mn ratio is preferably 1.0 to 2.0, more preferably 1.0 to 1.6.

[0562] Regarding the method for synthesizing the aforementioned polymeric surfactants, one method involves adding a polymerization initiator to a monomer containing unsaturated bonds and which imparts repeating units represented by the general formulas (7A) to (7E) and, as needed, other repeating units in an organic solvent, and then heating it to polymerize it. Examples of organic solvents used in polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Examples of polymerization initiators include AIBN, 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The preferred reaction temperature is 50–100°C. The preferred reaction time is 4–24 hours. Acid-labile groups can be directly introduced into the monomer, or they can be protected or partially protected after polymerization.

[0563] In the synthesis of the aforementioned polymeric surfactants, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol can be used to adjust the molecular weight. In this case, the amount of these chain transfer agents added is preferably 0.01 to 10 mol% relative to the total molar number of monomers polymerized.

[0564] When the chemically amplified resist composition of the present invention contains surfactant (E), its content is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 80 parts by mass of the base resin (A). If the content of surfactant (E) is 0.1 parts by mass or more, the receding contact angle between the resist film surface and water will be sufficiently improved; if it is 50 parts by mass or less, the dissolution rate of the resist film surface relative to the developer will be low, and the height of the formed fine pattern can be sufficiently maintained. Surfactant (E) can be used alone or in combination of two or more.

[0565] [(F) Other ingredients]

[0566] The chemically amplified resist composition of the present invention may also contain, as other components (F), compounds that produce acid due to acid decomposition (acid amplification compounds), organic acid derivatives, fluorinated alcohols, compounds with an Mw of 3,000 or less that change their solubility in the developer due to the action of acid (dissolution inhibitors), etc.

[0567] For the aforementioned acid-proliferating compounds, organic acid derivatives, fluorinated alcohols, and dissolution inhibitors, reference can be made to the compounds described in Japanese Patent Application Publication No. 2009-269953 or Japanese Patent Application Publication No. 2010-215608.

[0568] In the case of the aforementioned acid-proliferating compound, its content is preferably 0 to 5 parts by mass, and more preferably 0 to 3 parts by mass, relative to 80 parts by mass of the base resin (A). If the content is within this range, acid diffusion can be controlled, and there will be no distinguishable degradation or degradation of the pattern shape.

[0569] In the case of containing the aforementioned organic acid derivatives, the content of these derivatives is preferably 0 to 5 parts by mass, and more preferably 0 to 3 parts by mass, relative to 80 parts by mass of the base resin (A). If the content is within this range, acid diffusion can be controlled, which is ideal.

[0570] In the case of the aforementioned fluorinated alcohol, its content, relative to 80 parts by weight of the base resin (A), is preferably 0 to 5 parts by weight, and more preferably 0 to 3 parts by weight. If the content is within this range, development defects can be controlled, which is ideal.

[0571] When the aforementioned dissolution inhibitor is present, its content is preferably 0 to 5 parts by weight, and more preferably 0 to 3 parts by weight, relative to 80 parts by weight of the base resin (A). If the content is within this range, film loss after development can be controlled, which is ideal.

[0572] [Pattern Formation Method]

[0573] The pattern forming method of the present invention includes the following steps: forming a resist film on a substrate using the chemically amplified resist composition described above; exposing the aforementioned resist film to high-energy rays; and developing the aforementioned exposed resist film using a developing solution.

[0574] Regarding the aforementioned substrate, substrates such as those used for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective film, etc.) or substrates used for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) can be used.

[0575] The resist film can be formed by coating the aforementioned chemically amplified resist composition onto a substrate using methods such as spin coating, with a film thickness preferably of 0.05 to 2 μm, and pre-baking it on a hot plate under conditions preferably of 60 to 150°C for 1 to 10 minutes, more preferably of 80 to 140°C for 1 to 5 minutes.

[0576] Examples of high-energy rays used in the exposure of resist films include KrF excimer lasers, ArF excimer lasers, electron beams (EB), and extreme ultraviolet (EUV) rays with wavelengths of 3–15 nm. When using KrF excimer lasers, ArF excimer lasers, or EUV, the exposure uses a mask to form the desired pattern, and the exposure dose is preferably 1–200 mJ / cm². 2 Ideally, it should be 10–150 mJ / cm². 2 Irradiation is performed in this manner. When using EB, a mask is used to form the desired pattern, or the exposure is preferably 1–5000 μC / cm. 2 Ideally, the temperature should be between 10 and 2000 μC / cm. 2 Irradiation is performed in this manner.

[0577] Furthermore, in addition to the usual exposure method, an immersion method can be used, in which a liquid with a refractive index of 1.0 or higher is placed between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[0578] The aforementioned water-insoluble protective film, used to prevent leaching from the resist film and improve the hydrophobicity of the film surface, is broadly classified into two types. One type is an organic solvent-stripping type, which does not dissolve the resist film and requires stripping with an organic solvent before alkaline aqueous solution development. The other type is an alkaline aqueous solution-soluble type, which is soluble in alkaline developing solution and removes the protective film simultaneously with the removal of the soluble portion of the resist film. The latter is particularly preferably a material made from a polymer containing 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water but soluble in alkaline developing solution, and which is dissolved in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof. It is also possible to prepare a material by dissolving the aforementioned surfactants that are insoluble or sparingly soluble in water but soluble in alkaline developing solution in an alcohol solvent with 4 or more carbon atoms, an ether solvent with 8 to 12 carbon atoms, or a mixture thereof.

[0579] After exposure, baking (PEB) may be performed as needed. PEB can be performed, for example, by heating on a hot plate at a temperature preferably 60–200°C for 1–5 minutes, or more preferably 80–180°C for 1–3 minutes.

[0580] For example, a developing solution containing an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) of 0.1 to 5% by mass, more preferably 2 to 3% by mass, is used, and conventional methods such as dip, immersion, and spraying are employed for development, preferably for 0.1 to 3 minutes, more preferably 0.5 to 2 minutes. In this way, the exposed part dissolves and the desired pattern can be formed on the substrate.

[0581] Alternatively, pure water rinsing can be performed after the resist film is formed to extract acid-generating agents or wash away particles from the film surface. Rinsing can also be performed after exposure to remove water residue on the film.

[0582] In addition, a double patterning method can also be used to form patterns. Examples of double patterning methods include: a trenching method in which a 1:3 trench pattern is formed by processing a substrate with a 1:3 trench pattern through a first exposure and etching, offsetting the position, and forming a 1:3 trench pattern through a second exposure to form a 1:1 pattern; and a line method in which a 1:1 pattern with a halved pitch is formed by processing a first substrate with a 1:3 isolated residual pattern through a first exposure and etching, offsetting the position, and processing a second substrate with a 1:3 isolated residual pattern formed under the first substrate through a second exposure.

[0583] In the pattern forming method of the present invention, a negative tone development method can also be used, which uses an organic solvent as a developer instead of the aforementioned alkaline aqueous solution to dissolve the unexposed areas.

[0584] Regarding the organic solvents used in the aforementioned negative tone development, there are no particular limitations if they can be used as developing solutions for patterning. For example, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, and methyl valerate can be used. Esters, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc. These organic solvents can be used alone or in combination.

[0585] [Example]

[0586] The present invention will be specifically described below using examples and comparative examples, but the present invention is not limited thereto.

[0587] [1] Synthesis of polymeric monomers

[0588] [Example 1-1] Synthesis of monomer A1

[0589] [Chemistry 165]

[0590]

[0591] For a container containing 12.8 g of magnesium, a mixed solution of 105.4 g of 1-chloro-4-[(1-methylcyclopentyl)oxy]benzene, 0.9 g of dibromoethane, and 250 g of tetrahydrofuran (THF) was added dropwise under a nitrogen atmosphere. The Grignard reagent was prepared by maintaining an internal temperature above 60 °C while observing the exothermic reaction. Acetone was then added dropwise under ice bath cooling, and the mixture was matured at 50 °C for 2 hours. The reaction solution was quenched with dilute hydrochloric acid under ice bath cooling, and 250 g of n-hexane was added to extract the organic layer.

[0592] The obtained organic layer was washed with ultrapure water and then concentrated under reduced pressure. The residue was purified by reduced pressure distillation to obtain 88.0 g of intermediate A1 (distillation temperature 109℃ / 15Pa, yield 75%).

[0593] Next, 68.3 g of triethylamine, 4.6 g of 4-dimethylaminopyridine, and 200 g of acetonitrile were added to the obtained intermediate A1, and 54.9 g of methacrylamide chloride was added dropwise to this mixture at room temperature. After the reaction solution was matured for 12 hours, it was quenched with dilute hydrochloric acid, and then 200 g of toluene was added to extract the organic layer. The obtained organic layer was washed with ultrapure water, followed by concentration under reduced pressure, thereby obtaining 104.5 g of monomer A1 of the target compound in the form of an oil (yield 92.1%).

[0594] [Examples 1-2 to 1-7] Synthesis of monomers A2 to A7

[0595] Monomers A2 to A7, which are polymerizable monomers, are synthesized using corresponding raw materials and various organic synthesis reactions. The structures of monomers A2 to A7 are shown below.

[0596] [Chemistry 166]

[0597]

[0598] [2] Polymer synthesis

[0599] Among the monomers used in the synthesis of polymers, those other than monomers A1 to A7 are as follows.

[0600] [Chemistry 167]

[0601]

[0602] [Chemistry 168]

[0603]

[0604] [Chemistry 169]

[0605]

[0606] [Chemistry 170]

[0607]

[0608] [Example 2-1] Synthesis of Polymer P-1

[0609] In a nitrogen atmosphere, monomers A1 (89.2 g), b2-1 (24.8 g), c-1 (38.0 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) 3.96 g, and MEK 127 g were measured in a flask to prepare a monomer-polymerization initiator solution. In another flask under a nitrogen atmosphere, 46 g of MEK was measured, and the mixture was heated to 80°C with stirring. The aforementioned monomer-polymerization initiator solution was then added dropwise over 4 hours. After the addition was complete, the polymerization solution was maintained at 80°C and stirred for another 2 hours, followed by cooling to room temperature. The resulting polymerization solution was added dropwise to 2,000 g of vigorously stirred hexane, and the precipitated polymer was filtered. Further, the obtained polymer was washed twice with 600 g of hexane and then dried under vacuum at 50°C for 20 hours to obtain a white powdered polymer P-1 (yield 146 g, 96% yield). The Mw of polymer P-1 is 9,300, and the Mw / Mn ratio is 1.79. Furthermore, Mw is the converted value of polystyrene obtained by GPC using DMF as a solvent.

[0610] [Chemistry 171]

[0611]

[0612] [Examples 2-2 to 2-35, Comparative Examples 1-1 to 1-17] Synthesis of polymers P-2 to P-35 and comparative polymers CP-1 to CP-17

[0613] Except for changing the type and blending ratio of each monomer, the polymers shown in Tables 1 and 2 were synthesized using the same method as in Example 2-1.

[0614] [Table 1]

[0615]

[0616]

[0617] [Table 2]

[0618]

[0619]

[0620] [3] Preparation of chemically amplified resist composition

[0621] [Examples 3-1 to 3-39, Comparative Examples 2-1 to 2-21]

[0622] The polymers (P-1 to P-35), comparative polymers (CP-1 to CP-17), photoacid generators (PAG-X to PAG-Y), and quenchers (SQ-1 to SQ-3, AQ-1) of the present invention were dissolved in a solvent containing 0.01% by mass of surfactant A (OMNOVA) to prepare a solution. The solution was then filtered through a 0.2 μm Teflon (registered trademark) type filter to prepare chemically amplified resist compositions (R-1 to R-39, CR-1 to CR-21).

[0623] [Table 3]

[0624]

[0625]

[0626] [Table 4]

[0627]

[0628]

[0629] [Table 5]

[0630]

[0631]

[0632] The components are listed in Tables 3-5 as follows.

[0633] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate)

[0634] DAA (diacetone alcohol)

[0635] • Photoacid generators: PAG-X, PAG-Y

[0636] [Chemistry 172]

[0637]

[0638] Quenching agents: SQ-1~SQ-3, AQ-1

[0639] [Chemistry 173]

[0640]

[0641] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane-tetrahydrofuran-2,2-dimethyl-1,3-propanediol copolymer (manufactured by OMNOVA).

[0642] [Chemistry 174]

[0643]

[0644] a : (b + b') : (c + c') = 1 : 4 ~ 7 : 0.01 ~ 1 (molar ratio)

[0645] Mw = 1,500

[0646] [4] Evaluation of EUV lithography

[0647] [Examples 4-1 to 4-39, Comparative Examples 3-1 to 3-21]

[0648] The chemically amplified resist compositions shown in Tables 3-5 were spin-coated onto a Si substrate containing a silicon spin-coated hard mask SHB-A940 (43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd., with a film thickness of 20 nm. A resist film with a thickness of 35 nm was then pre-baked at 105°C for 60 seconds using a hot plate. The resist film was then exposed using an EUV scanning exposure machine NXE3400 (NA 0.33, σ 0.9 / 0.6, 90° dipole illumination, mask with a 1:1 line and spacing pattern with a pitch of 32 nm on the wafer) manufactured by ASML. The resist film was then subjected to PEB at the temperatures described in Tables 6-7 for 60 seconds on a hot plate, followed by development with a 2.38% by mass TMAH aqueous solution for 30 seconds to obtain a line and spacing pattern with a line size of 16 nm.

[0649] The exposure amount when the line size is formed at 16 nm was measured and defined as the sensitivity. The line refresh rate (LWR) was measured using a Hitachi High-Tech (CG6300) length-measuring SEM. Furthermore, the process window (PW) was calculated by subtracting the smallest line size from the largest line size that uses less exposure than the sensitivity of the resist film without line-like bridging, and the smallest line size that uses more exposure than the sensitivity of the resist film without resist pattern collapse or film loss. The results are presented in Tables 6 and 7.

[0650] [Table 6]

[0651]

[0652]

[0653] [Table 7]

[0654]

[0655] As can be seen from the results shown in Tables 6 and 7, Examples 4-1 to 4-39, which use chemically amplified resist compositions containing repeating units of polymeric compounds derived from the polymerizable monomers of the present invention, exhibit high sensitivity, low LWR, and a wide process window.

[0656] On the other hand, Comparative Examples 4-1 to 4-21, which use chemically amplified resist compositions CR-1 to CR-21 containing repeating units derived from monomers having only one type of acid-indestructible group but not the polymerizable monomers of the present invention, exhibit low sensitivity, high LWR, and a narrow process window.

[0657] This specification contains the following specifications.

[0658] [1]: A polymerizable monomer, characterized in that: each has one or more acid-instantaneous groups with different structures.

[0659] [2]: The polymerizable monomers as described in [1] above, wherein the polymerizable monomers are represented by the following general formula (A1);

[0660] [Chemistry 175]

[0661]

[0662] In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 It is a single bond or an aryl group; n is 0 or 1; AL 1 and AL 2 It is an unstable group in acids; however, AL 1 With AL 2 They have different structures.

[0663] [3]: Polymerizable monomers as described in [2] above, wherein the polymerizable monomers of the aforementioned general formula (A1) are represented by the following general formula (A1-1) or (A1-2);

[0664] [Chemistry 176]

[0665]

[0666] In the formula, R A X 1 , n, and AL 2 Same as above; R 11 R 21 and R 22Each group can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may contain heteroatoms; W1 represents an alicyclic hydrocarbon group; W2 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0667] [4]: The polymerizable monomers as described in [3] above, wherein the polymerizable monomers of the aforementioned general formula (A1-1) are represented by any one of the following general formulas (A2-1) and (A2-2), and the polymerizable monomers of the general formula (A1-2) are represented by any one of the following general formulas (A2-3) and (A2-4);

[0668] [Chemistry 177]

[0669]

[0670] In the formula, R A X 1 R 11 R 21 R 22 W1 and W2 are the same as described above; R 12 R 13 R 14 R 23 R 24 and R 25 Each is independently a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may also contain heteroatoms; W'11 and W'21 each independently represent an alicyclic hydrocarbon group; W'12 and W'22 each independently represent an alicyclic hydrocarbon group or an aromatic hydrocarbon group; m is 0 or 1; however, when W2 is an alicyclic hydrocarbon group, m is 1; when W2 is an aromatic hydrocarbon group, m is 0 or 1.

[0671] [5]: A polymeric compound characterized by containing repeating units obtained from polymerizable monomers of any one of [1] to [4] above.

[0672] [6]: The polymeric compound as described in [5] above, wherein the aforementioned polymeric compound further contains a repeating unit represented by the following general formula (b1);

[0673] [Chemistry 178]

[0674]

[0675] In the formula, R A Y is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; 1 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom in the main chain; R 30It can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; b is an integer from 1 to 4; c is an integer from 0 to 4; but, 1≤b+c≤5.

[0676] [7]: The polymeric compound as described in [5] or [6] above, wherein the polymeric compound further contains at least one of the repeating units represented by the following general formula (c1), the repeating units represented by the following general formula (c2), the repeating units represented by the following general formula (c3), and the repeating units represented by the following general formula (c4).

[0677] [Chemistry 179]

[0678]

[0679] In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 It is a single bond or a phenylene; Z 2 For *-C(=O)-OZ 21 -、*-C(=O)-NH-Z 21 - or *-OZ 21 -;Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 3 Each can be independently a single bond, phenylene, naphthylene, or *-C(=O)-OZ 31 -;Z 31 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms; the aforementioned aliphatic hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; Z 4 Each is independently a single bond, **-Z 41 -C(=O)-O-、**-C(=O)-NH-Z 41 - or **-OZ 41 -;Z 41 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 5 Each is independently a single bond, ***-Z 51 -C(=O)-O-、***-C(=O)-NH-Z 51 - or ***-OZ 51 -;Z 51 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 6It can be a single bond, methylene, ethylene, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, *-C(=O)-OZ 61 -、*-C(=O)-NH-Z 61 - or *-OZ 61 -;Z 61 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; * indicates an atomic bond with a carbon atom in the main chain; ** indicates an atomic bond with a Z atom. 3 atomic bonds; *** indicates the relationship with Z 4 atomic bonds; R 31 and R 32 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; furthermore, R 31 With R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; L 1 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, carbonate bond, or carbamate bond; Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; however, it does not contain all Rf atoms. 5 and Rf 6 The case where both are hydrogen atoms; M - It is a non-nucleophilic relative ion; A + It is an onium cation; d is an integer from 0 to 3.

[0680] [8]: A chemically amplified resist composition, characterized in that it contains a base resin composed of a polymeric compound as described in any of [5] to [7] above, and an organic solvent.

[0681] [9]: The chemically amplified resist composition as described in [8] above, wherein the aforementioned chemically amplified resist composition further contains one or more selected from quenching agents, photoacid generators, and surfactants.

[0682]

[10] : A pattern forming method, characterized by comprising the following steps:

[0683] A resist film is formed on a substrate using a chemically amplified resist composition as described in [8] or [9] above;

[0684] The aforementioned resist film was exposed to high-energy radiation; and

[0685] The previously exposed resist film was developed using a developing solution.

[0686]

[11] : The pattern forming method described in

[10] above, wherein a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm is used as the aforementioned high-energy ray.

[0687] Furthermore, the present invention is not limited to the embodiments described above. The embodiments described above are examples; any embodiment having a substantially the same structure as the technical concept described in the claims of the present invention and performing the same effect is included within the technical scope of the present invention.

Claims

1. A polymerizable monomer, characterized in that: Each has one or more acid-instable groups with different structures.

2. The polymerizable monomer according to claim 1, wherein, The polymerizable monomer is represented by the following general formula (A1); In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; X 1 It is a single bond or an aryl group; n is 0 or 1; AL 1 and AL 2 It is an unstable group in acids; however, AL 1 With AL 2 They have different structures.

3. The polymerizable monomer according to claim 2, wherein, The polymerizable monomer of the general formula (A1) is represented by the following general formula (A1-1) or (A1-2); In the formula, R A X 1 , n, and AL 2 Same as above; R 11 R 21 and R 22 Each group can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may contain heteroatoms; W1 represents an alicyclic hydrocarbon group; W2 represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

4. The polymerizable monomer according to claim 3, wherein, The polymerizable monomer of the general formula (A1-1) is represented by any one of the following general formulas (A2-1) and (A2-2), and the polymerizable monomer of the general formula (A1-2) is represented by any one of the following general formulas (A2-3) and (A2-4). In the formula, R A X 1 R 11 R 21 R 22 W1 and W2 are the same as described above; R 12 R 13 R 14 R 23 R 24 and R 25 Each is independently a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 40 carbon atoms that may also contain heteroatoms; W'11 and W'21 each independently represent an alicyclic hydrocarbon group; W'12 and W'22 each independently represent an alicyclic hydrocarbon group or an aromatic hydrocarbon group; m is 0 or 1; however, when W2 is an alicyclic hydrocarbon group, m is 1; when W2 is an aromatic hydrocarbon group, m is 0 or 1.

5. A polymer compound, characterized in that: It contains repeating units derived from the polymeric monomers according to any one of claims 1 to 4.

6. The polymer compound according to claim 5, wherein, The polymer also contains repeating units represented by the following general formula (b1); In the formula, R A Y is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; 1 It represents a single bond or *-C(=O)-O-; * indicates an atomic bond with a carbon atom in the main chain; R 30 It can be a halogen atom, hydroxyl group, nitro group, or a hydrocarbon group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon oxy group with 1 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl group with 2 to 20 carbon atoms containing heteroatoms, a hydrocarbon carbonyl oxy group with 2 to 20 carbon atoms containing heteroatoms, or a hydrocarbon oxy carbonyl group with 2 to 20 carbon atoms containing heteroatoms; b is an integer from 1 to 4; c is an integer from 0 to 4; but, 1≤b+c≤5.

7. The polymer compound according to claim 5, wherein, The polymer compound also contains at least one repeating unit selected from the repeating unit represented by the following general formula (c1), the repeating unit represented by the following general formula (c2), the repeating unit represented by the following general formula (c3), and the repeating unit represented by the following general formula (c4). In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 1 It is a single bond or a phenylene; Z 2 For *-C(=O)-OZ 21 -、*-C(=O)-NH-Z 21 - or *-OZ 21 -;Z 21 It is an aliphatic hydrocarbon group, phenylene group, or a divalent group obtained by combining them, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 3 Each can be independently a single bond, phenylene, naphthylene, or *-C(=O)-OZ 31 -;Z 31 It is an aliphatic hydrocarbon group, phenylene group, or naphthylene group having 1 to 10 carbon atoms; the aliphatic hydrocarbon group may also contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring; Z 4 Each is independently a single bond, **-Z 41 -C(=O)-O-、**-C(=O)-NH-Z 41 - or **-OZ 41 -;Z 41 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 5 Each is independently a single bond, ***-Z 51 -C(=O)-O-、***-C(=O)-NH-Z 51 - or ***-OZ 51 -; Z 51 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 6 It can be a single bond, methylene, ethylene, phenylene, fluorinated phenylene, or phenylene substituted with trifluoromethyl, *-C(=O)-OZ 61 -、*-C(=O)-NH-Z 61 - or *-OZ 61 -;Z 61 It is an aliphatic alkylene group, phenylene, fluorinated phenylene, or trifluoromethyl-substituted phenylene, having 1 to 6 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; * indicates an atomic bond with a carbon atom in the main chain; ** indicates an atomic bond with a Z atom. 3 atomic bonds; *** indicates the relationship with Z 4 atomic bonds; R 31 and R 32 Each can be an independent hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; furthermore, R 31 With R 32 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; L 1 It can be a single bond, ether bond, ester bond, carbonyl group, sulfonate bond, carbonate bond, or carbamate bond; Rf 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; Rf 5 and Rf 6 Each is independently a hydrogen atom, a fluorine atom, or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; however, it does not contain all Rf atoms. 5 and Rf 6 The case where both are hydrogen atoms; M - It is a non-nucleophilic relative ion; A + It is an onium cation; d is an integer from 0 to 3.

8. A chemically amplified resist composition, characterized in that: It contains a base resin composed of the polymer compound according to claim 5, and an organic solvent.

9. The chemically amplified resist composition according to claim 8, wherein, The chemically amplified resist composition also contains one or more selected from quenchers, photoacid generators, and surfactants.

10. A method for forming a pattern, characterized in that, Includes the following steps: A resist film is formed on a substrate using the chemically amplified resist composition according to claim 8; The resist film was exposed to high-energy radiation; and The exposed resist film was developed using a developer.

11. The pattern forming method according to claim 10, wherein, The high-energy ray can be obtained by using a KrF excimer laser, an ArF excimer laser, an electron beam, or extreme ultraviolet light with a wavelength of 3–15 nm.

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