Amine compound, chemically amplified resist composition and pattern forming method

Abstract

To provide a chemically amplified resist composition which exhibits high sensitivity and improved LWR and CDU regardless of whether it is positive or negative, and a pattern forming method using the same.SOLUTION: There are provided: an amine compound represented by the following formula (1); and the chemically amplified resist composition containing a quencher comprising the amine compound.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an amine compound, a chemically amplified resist composition, and a method of forming a pattern. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming finer at a rapid pace. In particular, the expansion of the logic memory market due to the spread of smartphones is driving miniaturization. The most advanced miniaturization technology is the mass production of 10nm node devices using double patterning with ArF immersion lithography, and preparations are underway for the mass production of 7nm node devices using double patterning for the next generation. Extreme ultraviolet (EUV) lithography is being considered as a candidate for the next-generation 5nm node.

[0003] While logic devices are becoming more miniaturized, flash memory devices have become devices with stacked gates called 3D-NAND, and the capacity is increasing by increasing the number of layers. As the number of layers increases, the hard masks used to process them become thicker, and the photoresist film also becomes thicker. The resist for logic devices is becoming thinner, while the resist for 3D-NAND is becoming thicker.

[0004] As miniaturization progresses and approaches the diffraction limit of light, the contrast of light decreases. This decrease in contrast of light causes a decrease in the resolution of hole and trench patterns and a decrease in focus margin in positive resist films. Increasing the thickness of resist films will restore the film thickness of resist films used for previous generation devices, but higher dimensional uniformity (CDU) is required, which cannot be met with previous photoresist compositions. In order to prevent a decrease in the resolution of resist patterns due to a decrease in the contrast of light caused by smaller dimensions, or to improve CDU when thickening resist films, attempts are being made to improve the dissolution contrast of resist films.

[0005] For chemically amplified positive resist compositions that contain an acid generator and generate an acid by irradiation with light or an electron beam (EB) to cause a deprotection reaction by the acid, and for chemically amplified negative resist compositions that cause a polarity change reaction or a crosslinking reaction by the acid, the addition of a quencher (acid diffusion controller) for the purpose of improving contrast by controlling the diffusion of the acid into unexposed areas has been very effective. For this reason, many amine quenchers have been proposed (Patent Documents 1 and 2).

[0006] The acid labile group used in the (meth)acrylate polymer for the ArF resist composition undergoes a deprotection reaction by using a photoacid generator that generates a sulfonic acid substituted with a fluorine atom at the α-position, but does not undergo a deprotection reaction by using an acid generator that generates a sulfonic acid or a carboxylic acid not substituted with a fluorine atom at the α-position. When a sulfonium salt or an iodonium salt that generates a sulfonic acid not substituted with a fluorine atom at the α-position is mixed with a sulfonium salt or an iodonium salt that generates a sulfonic acid not substituted with a fluorine atom at the α-position, the sulfonium salt or the iodonium salt that generates a sulfonic acid not substituted with a fluorine atom at the α-position undergoes ion exchange with the sulfonic acid not substituted with a fluorine atom at the α-position. The sulfonic acid substituted with a fluorine atom at the α-position generated by light is reverted to a sulfonium salt or an iodonium salt by ion exchange, so that the sulfonium salt or the iodonium salt of the sulfonic acid or the carboxylic acid not substituted with a fluorine atom at the α-position functions as a quencher. A resist composition has been proposed that uses a sulfonium salt or an iodonium salt that generates a carboxylic acid as a quencher (Patent Document 3).

[0007] The sulfonium salt type quencher and the iodonium salt type quencher are photodecomposable like the photoacid generator. That is, the amount of quencher is reduced in the exposed area. Since acid is generated in the exposed area, when the amount of quencher is reduced, the concentration of acid is relatively increased, which improves the contrast. However, since the acid diffusion in the exposed area cannot be suppressed, it becomes difficult to control the acid diffusion.

[0008] Sulfonium salt type quenchers and iodonium salt type quenchers absorb light with a wavelength of 193 nm, so when used in combination with sulfonium salt type and iodonium salt type acid generators, the light transmittance of the resist film decreases. As a result, the cross-sectional shape of the pattern after development becomes tapered, especially in resist films with a thickness of 100 nm or more. A highly transparent quencher is required for resist films with a thickness of 100 nm or more, especially 150 nm or more.

[0009] It is effective to lower the post-exposure bake (PEB) temperature to suppress the diffusion of acid. However, in this case, the dissolution contrast decreases, which causes degradation of the resolution and line edge roughness (LWR). There is a demand for a new concept resist composition that suppresses the diffusion of acid and exhibits high contrast.

[0010] Amine quenchers with polarity change due to acid catalyst have been proposed. Patent documents 4 and 5 propose amine quenchers with acid labile groups. In this case, a carboxylic acid is generated by a deprotection reaction with an acid of a tertiary ester in which a carbonyl group is arranged on the nitrogen atom side, and the alkali solubility is improved. However, in this case, the molecular weight on the nitrogen atom side cannot be increased, so the acid diffusion control ability is low and the effect of improving contrast is slight. Patent document 6 proposes a quencher in which an amino group is generated by a deprotection reaction of a tert-butoxycarbonyl group with an acid. This is a mechanism in which a quencher is generated by exposure to light, which is the opposite effect to increasing contrast. The contrast is improved by a mechanism in which the quencher disappears due to exposure to light or an acid, or a mechanism in which the quenching ability is reduced. Patent document 7 proposes a quencher in which an amine compound forms a ring with an acid to form a lactam structure. The activity of the acid changes and the contrast is improved by changing the strong base amine compound to a weak base lactam compound. Although the application of these amine quenchers has been shown to improve performance to a certain extent, it is still insufficient for advanced control of acid diffusion, and the development of quenchers with even better acid diffusion control capabilities is desired. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] JP 2001-194776 A [Patent Document 2] JP 2002-226470 A [Patent Document 3] International Publication No. 2008 / 066011 [Patent Document 4] Patent No. 4044741 [Patent Document 5] JP 2012-008550 A [Patent Document 6] Patent No. 3790649 [Patent Document 7] Patent No. 5617799 Summary of the Invention [Problem to be solved by the invention]

[0012] In chemically amplified resist compositions using an acid catalyst, it is desirable to develop a quencher that can improve the LWR of line patterns and the CDU of hole patterns while also improving sensitivity. To achieve this, it is necessary to further reduce the diffusion distance of the acid and simultaneously improve the contrast, which are contradictory properties.

[0013] The present invention has been made in consideration of the above circumstances, and has an object to provide a chemically amplified resist composition which has high sensitivity and improved LWR and CDU, whether positive or negative, and a pattern formation method using the same. [Means for solving the problem]

[0014] As a result of extensive investigations to achieve the above-mentioned object, the present inventors have found that by using an amine compound having a highly polar ring structure and an acid labile group in the same molecule as a quencher, it is possible to obtain a chemically amplified resist composition which has improved LWR and CDU, high contrast, excellent resolution and a wide process margin, and have thus completed the present invention.

[0015] That is, the present invention provides the following amine compound, chemically amplified resist composition, and pattern forming method. 1. An amine compound represented by the following formula (1): [ka] (In the formula, m is an integer of 0 to 10. R N1 and R N2 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with halogen atoms, and -CH 2 - may be replaced by -O- or -C(=O)-. N1 and R N2 may be bonded to each other to form a ring together with the nitrogen atom to which they are attached, and the ring may contain -O- or -S-. N1 and R N2 cannot simultaneously become a hydrogen atom. X L is a hydrocarbylene group having 1 to 40 carbon atoms which may contain a heteroatom. L a1 is a single bond, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond or a carbamate bond. Ring R R1 is a (m+2)-valent heterocyclic group having 2 to 20 carbon atoms and having a lactone structure, lactam structure, sultone structure or sultam structure. R 1 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. When m is 2 or more, each R 1may be the same or different, and there may be two or more R 1 are combined together to form R R1 It may form a ring together with the above atoms. R AL is an acid labile group. 2. An amine compound 1 represented by the following formula (1A): [ka] (In the formula, m, L , L a1 , R R1 , R 1 and R AL is the same as above. Ring R R2 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms formed together with the nitrogen atom in the formula, and -CH 2 - may be replaced by -O- or -S-. 3. An amine compound represented by the following formula (1B): [ka] (In the formula, m, L , L a1 , R R1 , R R2 and R 1 teeth , same as above. n is an integer from 0 to 20. Ring R R3 represents the carbon atom C in the formula A and the ring is formed with -CH 2 - may be substituted with a group containing a heteroatom. R 2 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. When n is 2 or more, 2 or more R 2 may be the same or different, and there may be two or more R 2 may be bonded to each other to form a ring structure. R 3is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 4. (A) A chemically amplified resist composition comprising a quencher consisting of an amine compound according to any one of 1 to 3. 5. The chemically amplified resist composition according to 4, further comprising (B) a base polymer having a repeating unit represented by the following formula (a1) or (a2): [ka] (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX 11 - and X 11 is an alkanediyl group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or naphthylene group. X 2 is a single bond or *-C(=O)-O-. * indicates a bond to a carbon atom in the main chain. AL 1 and A.L. 2 are each independently an acid labile group. R 11 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. a is an integer from 0 to 4. 6. The chemically amplified resist composition of 4 or 5, wherein the base polymer contains a repeating unit represented by the following formula (b1) or (b2): [ka] (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A pis a hydrogen atom, or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride (-C(=O)-OC(=O)-). Y 1 is a single bond or *-C(=O)-O-. * represents a bond to a carbon atom in the main chain. R 12 represents a halogen atom, a cyano group, a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms which may contain a heteroatom, or a hydrocarbylcarbonyl group having 2 to 20 carbon atoms which may contain a heteroatom. b is an integer from 1 to 4; c is an integer from 0 to 4, provided that 1≦b+c≦5. 7. The chemically amplified resist composition according to any one of 4 to 6, wherein the base polymer contains a repeating unit represented by any one of the following formulas (c1) to (c3): [ka] (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 is a single bond or a phenylene group. Z 2 is *-C(=O)-OZ 21 -, *-C(=O)-NH-Z 21 -or*-OZ 21 -It is. 21 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. Z 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OZ 31 -It is. 31is an aliphatic hydrocarbylene group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or naphthylene group. Z 4 is a single bond or *-Z 41 -C(=O)-O-. Z 41 is a hydrocarbylene group having 1 to 20 carbon atoms which may contain a heteroatom. Z 5 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-C(=O)-OZ 51 -, *-C(=O)-NH-Z 51 -or * -OZ 51 -It is. 51 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * indicates a bond to a carbon atom in the main chain. R 21 and R 22 R is each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21 and R 22 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. L 11 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. Rf 1 and Rf 2 are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. Rf 3 and Rf 4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. M - is a non-nucleophilic counterion. A +is an onium cation. d is an integer from 0 to 3. 8. Any one of the chemically amplified resist compositions according to 4 to 7, further comprising (C) an organic solvent. 9. Any of the chemically amplified resist compositions of 4 to 8, further comprising (D) a photoacid generator. 10. The chemically amplified resist composition according to any one of 4 to 9, further comprising (E) a quencher other than the amine compound represented by formula (1). 11. Any of the chemically amplified resist compositions of 4 to 10, further comprising (F) a surfactant. 12. A pattern forming method comprising the steps of forming a resist film on a substrate using any one of the chemically amplified resist compositions according to 4 to 11, exposing the resist film to KrF excimer laser light, ArF excimer laser light, EB or EUV, and developing the exposed resist film using a developer. 13. A pattern formation method according to claim 12, in which an alkaline aqueous solution is used as a developer to dissolve exposed areas and obtain a positive pattern in which unexposed areas do not dissolve. 14. A pattern formation method according to claim 12, in which an organic solvent is used as a developer to dissolve the unexposed areas and obtain a negative pattern in which the exposed areas do not dissolve. 15. The method for forming a pattern according to any one of 12 to 14, wherein the exposure is immersion exposure performed by interposing a liquid having a refractive index of 1.0 or more between the resist film and a projection lens. 16. The pattern forming method according to claim 15, further comprising forming a protective film on the resist film, and carrying out immersion exposure by placing the liquid between the protective film and a projection lens. Effect of the Invention

[0016] The amine compound of the present invention has a highly polar lactone ring or sultone ring and an acid labile group in the same molecule, and functions as a quencher when used as a chemically amplified resist composition. Since it has an acid labile group, the exposed part is decomposed by an acid, and the polarity is changed, thereby improving the contrast. In addition, since it has a highly polar lactone ring or sultone ring in the molecule, it has a high proton affinity and a high boiling point of the compound itself, and is not easily volatilized during the heating process, so that it remains in the resist film and can effectively trap the generated acid. These synergistic effects make it possible to construct a chemically amplified resist composition with good sensitivity and improved LWR and CDU. [Brief description of the drawings]

[0017] [Figure 1] 1 is a 1H-NMR spectrum of compound AQ-1 synthesized in Example 1-1. [Diagram 2] 1 is a 1H-NMR spectrum of compound AQ-2 synthesized in Example 1-2. [Diagram 3] 1 is a 1H-NMR spectrum of compound AQ-3 synthesized in Example 1-3. [Figure 4] 1H-NMR spectrum of compound AQ-4 synthesized in Example 1-4. [Diagram 5] 1H-NMR spectrum of compound AQ-5 synthesized in Example 1-5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] [Amine compounds] The amine compound of the present invention is represented by the following formula (1). [ka]

[0019] In the formula (1), m is an integer of 0 to 10.

[0020] In formula (1), R N1 and RN2 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with halogen atoms, and -CH 2 - may be replaced by -O- or -C(=O)-. N1 and R N2 may be bonded to each other to form a ring together with the nitrogen atom to which they are attached, and the ring may contain -O- or -S-. N1 and R N2 cannot simultaneously become a hydrogen atom.

[0021] R N1 and R N2 The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl groups; and groups obtained by combining these groups.

[0022] R N1 and R N2 The ring that can be formed by bonding to each other together with the nitrogen atom to which they are bonded is preferably an alicyclic ring, and examples thereof include, but are not limited to, an aziridine ring, an azetidine ring, a pyrrolidine ring, and a piperidine ring. 2 - may be replaced by -O- or -S-.

[0023] In formula (1), X L is a hydrocarbylene group having 1 to 40 carbon atoms which may contain a heteroatom. Specific examples thereof include, but are not limited to, those shown below. In the following formulas, * represents L a1 and represents a bond to a nitrogen atom. [ka]

[0024] [ka]

[0025] [ka]

[0026] Of these, X L -0~X L -22 and X L -47~X L -49 is preferred, X L -0~X L -17 is more preferred.

[0027] In formula (1), L a1 is a single bond, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond or a carbamate bond. Among these, a single bond, an ether bond or an ester bond is preferred, and an ether bond or an ester bond is more preferred.

[0028] In formula (1), ring R R1 is a (m+2)-valent heterocyclic group having 2 to 20 carbon atoms and a lactone structure, lactam structure, sultone structure or sultam structure. The heterocyclic group may be either a single ring or a condensed ring, but is preferably a condensed ring from the viewpoints of raw material procurement and increasing the boiling point of the compound.

[0029] Specific examples of the heterocyclic group where m=0 include, but are not limited to, the groups shown below. In the following formulae, * represents L a1 and represents a bond to the carbon atom in -C(=O)O-. [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] In formula (1), R 1 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-pentyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group; a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, and a tricyclo[5.2.1.0 2,6]Cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as decanyl group, adamantyl group, and adamantylmethyl group; aryl groups having 6 to 20 carbon atoms, such as phenyl group, naphthyl group, and anthracenyl group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbyl groups may be substituted with groups containing heteroatoms, such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and the -CH 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a carbamate bond, an amide bond, an imide bond, a lactone ring, a sultone ring, a thiolactone ring, a lactam ring, a sultam ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group or the like.

[0034] When m is 2 or more, R is 2 or more 1 may be the same or different, and there may be two or more R 1 are combined together to form R R1 In this case, the ring may be formed together with the atoms forming R. Examples of the ring formed in this case include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a norbornane ring, and an adamantane ring. R1 Two R's bonded to the same atom form 1 may be bonded to each other to form a ring, forming a spiro ring.

[0035] In formula (1), R AL is an acid labile group. The acid labile group is preferably a tertiary hydrocarbyl group or a group that forms an acetal structure together with the adjacent oxygen atom, and is particularly preferably a tertiary hydrocarbyl group.

[0036] The tertiary hydrocarbyl group preferably has 4 to 20 carbon atoms, and more preferably has 4 to 15 carbon atoms. Specific examples thereof include, but are not limited to, those shown below. In the following formula, * represents a bond to an oxygen atom. [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] Examples of the group that forms the acetal structure include those represented by the formula (L1) described below. Specific examples of the group that forms the acetal structure include, but are not limited to, those shown below. In the following formula, * represents a bond to an oxygen atom. [ka]

[0041] [ka]

[0042] [ka]

[0043] The amine compound represented by formula (1) is preferably one represented by the following formula (1A). [ka] (In the formula, m, L , L a1 , R R1 , R R2 , R 1 and R AL is the same as above.)

[0044] In formula (1A), ring R R2 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms formed together with the nitrogen atom in the formula, and -CH 2 - may be substituted with -O- or -S-. R2 As for the -CH in the ring, 2 The - is preferably an alicyclic hydrocarbon group having 3 to 20 carbon atoms substituted with -O- or -S-.

[0045] The amine compound represented by formula (1A) is preferably one represented by the following formula (1B). [ka] (In the formula, m, L , L a1 , R R1 , R R2 and R 1 teeth , same as above.)

[0046] In formula (1B), n is an integer of 0 to 20. Ring R R3 represents the carbon atom C in the formula A and the ring is formed with -CH 2 - may be substituted with a group containing a heteroatom. 2 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. When n is 2 or more, 2 or more R 2 may be the same or different, and there may be two or more R 2 may be bonded to each other to form a ring structure. 3 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0047] Ring R R3 As the alicyclic hydrocarbon group represented by the following formula: a cyclopentane ring, a cyclohexane ring, or an adamantane ring is particularly preferred.

[0048] Examples of the amine compound represented by formula (1) include, but are not limited to, those shown below. [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057]

change

[0058]

change

[0059]

change

[0060]

change

[0061]

change

[0062]

change

[0063]

change

[0064]

change

[0065]

change

[0066]

change

[0067]

change

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] The amine compound of the present invention can be produced, for example, according to the following scheme. [ka] (In the formula, R N1 , R N2 , m, X L , L a1 , R R1 , R 1 and R AL is the same as above. X hal is a chlorine atom, a bromine atom, or an iodine atom.

[0076] That is, the amine compound represented by formula (1) can be synthesized by a substitution reaction between an intermediate In-A, which can be synthesized by a known synthesis method, and a primary or secondary amine.

[0077] The synthesis can be carried out by a known organic synthesis method. Specifically, intermediate In-A is dissolved in a polar aprotic solvent such as acetone, acetonitrile, dimethylformamide, or dimethylsulfoxide, and a primary or secondary amine is added to carry out the reaction. hal When is a chlorine atom or a bromine atom, the reaction can be accelerated by adding a catalytic amount of an alkali metal or quaternary ammonium iodide. Examples of the alkali metal iodide include sodium iodide and potassium iodide. Examples of the quaternary ammonium iodide include tetraethylammonium iodide and benzyltrimethylammonium iodide. The reaction temperature is preferably in the range from room temperature to the boiling point of the solvent used. The reaction time is usually about 30 minutes to 20 hours, although it is desirable to follow the reaction by gas chromatography (GC) or silica gel thin layer chromatography (TLC) in terms of yield and complete the reaction. The amine compound represented by formula (1) can be obtained by carrying out a normal aqueous work-up from the reaction mixture. The obtained amine compound can be purified according to a normal method such as chromatography or recrystallization, if necessary.

[0078] The above-mentioned production method is merely an example, and the production method of the amine compound of the present invention is not limited thereto.

[0079] [Chemically amplified resist composition] The chemically amplified resist composition of the present invention contains, as an essential component, a quencher consisting of an amine compound (A) represented by formula (1). In the present invention, the quencher is a material that traps the acid generated by the photoacid generator in the chemically amplified resist composition, thereby preventing the acid from diffusing into unexposed areas and forming a desired pattern.

[0080] The structural features of the amine compound of the present invention include a heterocycle having a highly polar lactone structure, lactam structure, sultone structure or sultam structure, and an acid labile group in the same molecule. The highly polar heterocycle structure increases the boiling point of the molecule, suppressing the volatilization of the amine compound in the heating step after the application of the resist composition, and dispersing the amine compound in the film. In addition, since the lipophilic acid labile group is in a bonded state before exposure, the amine compound is highly soluble in a solvent, but after exposure, the deprotection reaction of the acid labile group proceeds to generate a hydrophilic carboxylic acid. This improves the dissolution contrast between the exposed and unexposed areas. In the exposed area, in the case of a positive resist composition, the affinity with an alkaline developer is high, making it possible to form a pattern with few development defects. In the case of a negative resist composition, the solubility in an organic solvent developer is small, making the residual film characteristics excellent. These synergistic effects effectively quench the acid generated from the acid generator, and the development characteristics are also excellent, making it possible to form a pattern with high sensitivity and improved LWR and CDU.

[0081] In the chemically amplified resist composition of the present invention, the content of the quencher consisting of the amine compound represented by formula (A) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, relative to 80 parts by mass of the base polymer (B) described below. If the content of the quencher (A) is within the above range, the sensitivity and resolution are good, and there is no risk of problems with foreign matter occurring after development of the resist film or during stripping, which is preferable. The quencher (A) may be used alone or in combination of two or more types.

[0082] [(B) Base polymer] The chemically amplified resist composition of the present invention may contain a base polymer (B). The base polymer of component (B) contains a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2). [ka]

[0083] In formulas (a1) and (a2), R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 1 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OX 11 - and X 11 X is an alkanediyl group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 2 is a single bond or *-C(=O)-O-. * represents a bond to a carbon atom in the main chain. AL 1 and A.L. 2 are each independently an acid labile group.

[0084] In formula (a2), R 11 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 1 Examples of the hydrocarbyl group having 1 to 20 carbon atoms include the same ones as those exemplified above as the hydrocarbyl group having 1 to 20 carbon atoms and represented by the following formula: a is an integer of 0 to 4, and preferably 0 or 1.

[0085] X in formula (a1) 1 Examples of structures in which R is changed include, but are not limited to, those shown below. A and A.L. 1 is the same as above. [ka]

[0086] [ka]

[0087] A polymer containing the repeating unit a1 is decomposed by the action of an acid to produce a carboxyl group, and becomes alkali-soluble.

[0088] AL 1 and A.L. 2 The acid labile group represented by the formula (I) is not particularly limited, but preferred examples include groups selected from the following formulae (L1) to (L4), tertiary hydrocarbyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl groups in which each alkyl group has 1 to 6 carbon atoms, carbonyl groups, and saturated hydrocarbyl groups having 4 to 20 carbon atoms and containing an ether bond or an ester bond. [ka] (In the formula, * represents a bond.)

[0089] In formula (L1), R L01 and R L02 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 18 carbon atoms. The saturated hydrocarbyl group may be linear, branched or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-octyl and 2-ethylhexyl groups; and cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, norbornyl, tricyclodecanyl, tetracyclododecanyl and adamantyl groups. The saturated hydrocarbyl group preferably has 1 to 10 carbon atoms.

[0090] R L03 is a hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and may contain a group containing a heteroatom. The hydrocarbyl group may be saturated or unsaturated and may be linear, branched, or cyclic, but is preferably a saturated hydrocarbyl group. In addition, some or all of the hydrogen atoms of the saturated hydrocarbyl group may be substituted with a hydroxy group, a saturated hydrocarbyloxy group, an oxo group, an amino group, a saturated hydrocarbylamino group, or the like, and the -CH constituting the saturated hydrocarbyl group may be substituted with a hydroxy group, a saturated hydrocarbyloxy group, an oxo group, an amino group, a saturated hydrocarbylamino group, or the like. 2A part of - may be substituted with a group containing a heteroatom such as an oxygen atom. L01 and R L02 Examples of the saturated hydrocarbyl group represented by the formula (I) include the same as those mentioned above. Examples of the substituted saturated hydrocarbyl group include the groups shown below. [ka] (In the formula, * represents a bond.)

[0091] R L01 , R L02 and R L03 Any two of R may be bonded to each other to form a ring together with the carbon atom or the carbon atom and oxygen atom to which they are bonded. When a ring is formed, R L01 , R L02 and R L03 are each independently an alkanediyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

[0092] In formula (L2), R L04 is a tertiary hydrocarbyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, a carbonyl group, a saturated hydrocarbyl group containing an ether bond or an ester bond and having 4 to 20 carbon atoms, or a group represented by formula (L1). x is an integer of 0 to 6.

[0093] R L04The tertiary hydrocarbyl group represented by the formula (I) may be branched or cyclic, and specific examples thereof include tert-butyl, tert-pentyl, 1,1-diethylpropyl, 2-cyclopentylpropan-2-yl, 2-cyclohexylpropan-2-yl, 2-(bicyclo[2.2.1]heptan-2-yl)propan-2-yl, 2-(adamantan-1-yl)propan-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, and 2-ethyl-2-adamantyl. The trialkylsilyl group includes trimethylsilyl, triethylsilyl, and dimethyl-tert-butylsilyl. Examples of the saturated hydrocarbyl group containing a carbonyl group, an ether bond or an ester bond include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolan-5-yl group.

[0094] In formula (L3), R L05is an optionally substituted saturated hydrocarbyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. The optionally substituted saturated hydrocarbyl group may be linear, branched or cyclic, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl and n-hexyl groups; cyclic saturated hydrocarbyl groups such as cyclopentyl and cyclohexyl groups; and groups in which some or all of the hydrogen atoms have been substituted with a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a carboxy group, a saturated hydrocarbylcarbonyl group having 1 to 6 carbon atoms, an oxo group, an amino group, a saturated hydrocarbylamino group having 1 to 6 carbon atoms, a cyano group, a mercapto group, a saturated hydrocarbylthio group having 1 to 6 carbon atoms, a sulfo group or the like. Examples of the optionally substituted aryl group include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and groups in which some or all of the hydrogen atoms of these groups have been substituted with a hydroxy group, a saturated hydrocarbyloxy group having 1 to 10 carbon atoms, a carboxy group, a saturated hydrocarbylcarbonyl group having 1 to 10 carbon atoms, an oxo group, an amino group, a saturated hydrocarbylamino group having 1 to 10 carbon atoms, a cyano group, a mercapto group, a saturated hydrocarbylthio group having 1 to 10 carbon atoms, a sulfo group, or the like.

[0095] In formula (L3), y is 0 or 1; z is an integer of 0 to 3; and 2y+z=2 or 3.

[0096] In formula (L4), R L06 is an optionally substituted saturated hydrocarbyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. Specific examples of the optionally substituted saturated hydrocarbyl group and the optionally substituted aryl group include R L05 Examples of the compound represented by the formula (I) include the same compounds as those exemplified above.

[0097] R L07 ~R L16are each independently a hydrogen atom or an optionally substituted hydrocarbyl group having 1 to 15 carbon atoms. The hydrocarbyl group may be saturated or unsaturated and may be linear, branched, or cyclic, although a saturated hydrocarbyl group is preferred. Examples of the hydrocarbyl group include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl; cyclic saturated hydrocarbyl groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, and cyclohexylbutyl; and groups in which some or all of the hydrogen atoms of these groups have been substituted with a hydroxy group, a saturated hydrocarbyloxy group having 1 to 10 carbon atoms, a carboxy group, a saturated hydrocarbyloxycarbonyl group having 1 to 10 carbon atoms, an oxo group, an amino group, a saturated hydrocarbylamino group having 1 to 10 carbon atoms, a cyano group, a mercapto group, a saturated hydrocarbylthio group having 1 to 10 carbon atoms, or a sulfo group. L07 ~R L16 Two selected from these may be bonded to each other to form a ring together with the carbon atom to which they are bonded (for example, R L07 and R L08 , R L07 and R L09 , R L07 and R L10 , R L08 and R L10 , R L09 and R L10 , R L11 and R L12 , R L13 and R L14 In this case, the group participating in the ring formation is a hydrocarbylene group having 1 to 15 carbon atoms. Examples of the hydrocarbylene group include those obtained by removing one hydrogen atom from the above-mentioned examples of the hydrocarbyl group. L07 ~R L16 may bond to adjacent carbon atoms without any intermediate bond to form a double bond (for example, R L07 and R L09 , RL09 and R L15 , R L13 and R L15 , R L14 and R L15 etc.).

[0098] Among the acid labile groups represented by formula (L1), linear or branched ones include the groups shown below, but are not limited to these. [ka] (In the formula, * represents a bond.)

[0099] Among the acid labile groups represented by formula (L1), examples of cyclic groups include a tetrahydrofuran-2-yl group, a 2-methyltetrahydrofuran-2-yl group, a tetrahydropyran-2-yl group, and a 2-methyltetrahydropyran-2-yl group.

[0100] Examples of the acid labile group represented by formula (L2) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-pentyloxycarbonyl group, a tert-pentyloxycarbonylmethyl group, a 1,1-diethylpropyloxycarbonyl group, a 1,1-diethylpropyloxycarbonylmethyl group, a 1-ethylcyclopentyloxycarbonyl group, a 1-ethylcyclopentyloxycarbonylmethyl group, a 1-ethyl-2-cyclopentenyloxycarbonyl group, a 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

[0101] Examples of the acid labile group represented by formula (L3) include a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-n-propylcyclopentyl group, a 1-isopropylcyclopentyl group, a 1-n-butylcyclopentyl group, a 1-sec-butylcyclopentyl group, a 1-cyclohexylcyclopentyl group, a 1-(4-methoxy-n-butyl)cyclopentyl group, a 1-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 3-methyl-1-cyclopenten-3-yl group, a 3-ethyl-1-cyclopenten-3-yl group, a 3-methyl-1-cyclohexen-3-yl group, and a 3-ethyl-1-cyclohexen-3-yl group.

[0102] As the acid labile group represented by formula (L4), groups represented by the following formulae (L4-1) to (L4-4) are particularly preferred. [ka]

[0103] In the formulae (L4-1) to (L4-4), ** represents the bonding position and bonding direction. L41 are each independently a hydrocarbyl group having 1 to 10 carbon atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic, but is preferably a saturated hydrocarbyl group. Examples of the hydrocarbyl group include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, and n-hexyl groups; and cyclic saturated hydrocarbyl groups such as cyclopentyl and cyclohexyl groups.

[0104] The groups represented by formulae (L4-1) to (L4-4) may have stereoisomers (enantiomers or diastereomers), and formulae (L4-1) to (L4-4) represent all of these stereoisomers. When the acid labile group is a group represented by formula (L4), it may contain multiple stereoisomers.

[0105] For example, formula (L4-3) represents one or a mixture of two selected from groups represented by the following formulae (L4-3-1) and (L4-3-2). [ka] (In the formula, R L41 and ** are the same as above.)

[0106] Moreover, the formula (L4-4) represents one or a mixture of two or more selected from the groups represented by the following formulae (L4-4-1) to (L4-4-4). [ka] (In the formula, R L41 and ** are the same as above.)

[0107] Formulae (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and (L4-4-1) to (L4-4-4) are also intended to represent their enantiomers and mixtures of enantiomers.

[0108] In addition, the bonding directions of the formulae (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and (L4-4-1) to (L4-4-4) are on the exo side of the bicyclo[2.2.1]heptane ring, respectively, thereby realizing high reactivity in the acid-catalyzed elimination reaction (see JP 2000-336121 A). In the production of a monomer having a tertiary exo-saturated hydrocarbyl group having a bicyclo[2.2.1]heptane skeleton as a substituent, a monomer substituted with an endo-alkyl group represented by the following formulae (L4-1-endo) to (L4-4-endo) may be included, but in order to realize good reactivity, the exo ratio is preferably 50 mol% or more, and more preferably 80 mol% or more. [ka] (In the formula, R L41 and ** are the same as above.)

[0109] Examples of the acid labile group represented by formula (L4) include, but are not limited to, the groups shown below. [ka] (In the formula, ** is the same as above.)

[0110] Also, AL 1 and A.L. 2 Among the acid labile groups represented by the formula (I), the tertiary hydrocarbyl group having 4 to 20 carbon atoms, the trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, and the saturated hydrocarbyl group having 4 to 20 carbon atoms and containing a carbonyl group, an ether bond or an ester bond are each represented by the formula (I): L04 Examples of the examples are similar to those given in the description of .

[0111] Examples of the repeating unit a1 include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] These specific examples are X 1is a single bond, but X 1 Even when X is other than a single bond, it can be combined with a similar acid labile group. 1 Specific examples of when is other than a single bond are as described above.

[0117] A polymer containing the repeating unit a2 is decomposed by the action of an acid to generate a hydroxyl group, similar to the repeating unit a1, and becomes soluble in an alkali. Examples of the repeating unit a2 include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0118] [ka]

[0119] The base polymer preferably further contains a repeating unit represented by the following formula (b1) (hereinafter also referred to as repeating unit b1) or a repeating unit represented by the following formula (b2) (hereinafter also referred to as repeating unit b2). [ka]

[0120] In formulas (b1) and (b2), R A are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. p is a hydrogen atom, or a polar group containing at least one structure selected from a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride (-C(=O)-OC(=O)-). 1 is a single bond or *-C(=O)-O-. * represents a bond to a carbon atom in the main chain. R 12is a halogen atom, a cyano group, a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom, a hydrocarbyloxy group having 1 to 20 carbon atoms which may contain a heteroatom, or a hydrocarbylcarbonyl group having 2 to 20 carbon atoms which may contain a heteroatom. b is an integer of 1 to 4. c is an integer of 0 to 4, with the proviso that 1≦b+c≦5.

[0121] Examples of the repeating unit b1 include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129]

change

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139] Examples of the repeating unit b2 include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0140] [ka]

[0141] As the repeating unit b1 or b2, in ArF lithography, those having a lactone ring as a polar group are particularly preferred, while in KrF lithography, EB lithography and EUV lithography, those having a phenol moiety are preferred.

[0142] The base polymer may further contain a repeating unit represented by any one of the following formulas (c1) to (c3) (hereinafter also referred to as repeating units c1 to c3, respectively). These are units that function as a photoacid generator, and when a base polymer containing these is used, the blending of the photoacid generator (D), which will be described later, may be omitted. [ka]

[0143] In formulas (c1) to (c3), R A is the same as above. Z 1 is a single bond or a phenylene group. 2 is *-C(=O)-OZ 21 -, *-C(=O)-NH-Z 21 -or*-OZ 21 -It is. 21 Z is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-OZ 31-It is. 31 Z is an aliphatic hydrocarbylene group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. 4 is a single bond or **-Z 41 -C(=O)-O-. Z 41 Z is a hydrocarbylene group having 1 to 20 carbon atoms which may contain a heteroatom. 5 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-C(=O)-OZ 51 -, *-C(=O)-NH-Z 51 -or * -OZ 51 -It is. 51 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. * represents a bond to a carbon atom in the main chain. ** represents Z 3 Represents a bond with .

[0144] In formula (c1), R 21 and R 22 R is each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 21 and R 22 may be bonded to each other to form a ring together with the sulfur atom to which they are attached.

[0145] R 21 and R 22The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl groups; and groups obtained by combining these groups. Among these, an aryl group is preferred. In addition, a part or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and the -CH 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0146] Examples of the cation of the repeating unit c1 include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0147] [ka]

[0148] In formula (c1), M - is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as mesylate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; and methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0149] Other examples of the non-nucleophilic counter ion include a sulfonate anion represented by the following formula (c1-1) in which the α-position is substituted with a fluorine atom, and a sulfonate anion represented by the following formula (c1-2) in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group. [ka]

[0150] In formula (c1-1), R 23 is a hydrogen atom or a hydrocarbyl group, and the hydrocarbyl group may contain an ether bond, an ester bond, a carbonyl group, a lactone ring, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111 Examples of the examples are similar to those given in the description of .

[0151] In formula (c1-2), R 24is a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbylcarbonyl group having 6 to 20 carbon atoms, and the hydrocarbyl group and the hydrocarbylcarbonyl group may contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbyl group and the hydrocarbylcarbonyl group may have a hydrocarbyl moiety that is saturated or unsaturated and may be linear, branched, or cyclic. Specific examples thereof include R in the formula (2A') described below. 111 Examples of the examples are similar to those given in the description of .

[0152] Specific examples of the sulfonate anion represented by the non-nucleophilic counter ion include, but are not limited to, those shown below. 25 is a hydrogen atom, a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms, and Ac is an acetyl group. [ka]

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] In formula (c2), Z 41 Examples of the hydrocarbylene group having 1 to 20 carbon atoms and optionally containing a heteroatom, represented by the following, include, but are not limited to, the following: [ka] (In the formula, the dashed lines represent bonds.)

[0161] In formula (c2), L 11 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond.

[0162] In formula (c2), Rf 1 and Rf 2 Rf are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms, and are preferably all fluorine atoms in order to increase the acid strength of the generated acid. 3 and Rf 4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms, and in order to improve solubility in a solvent, it is preferable that at least one of them is a trifluoromethyl group. d is an integer of 0 to 3, and is particularly preferably 1.

[0163] Examples of the anion of the repeating unit represented by formula (c2) include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] Specific examples of the anion of the repeating unit represented by formula (c3) include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0168] In formulas (c2) and (c3), A + is an onium cation. Examples of the onium cation include a sulfonium cation, an iodonium cation, and an ammonium cation. The onium cation is preferably a sulfonium cation or an iodonium cation, and more preferably a sulfonium cation represented by the following formula (c4) or an iodonium cation represented by the following formula (c5). [ka]

[0169] In formulas (c4) and (c5), R 31 ~R 35are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl groups; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclohexenyl groups; aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl groups; and groups obtained by combining these groups. Of these, aryl groups are preferred. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and the -CH 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0170] R 31 and R 32 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, examples of the sulfonium cation represented by formula (c4) include those represented by the following formula: [ka] (In the formula, the dashed line represents R 33 It represents a bond with .)

[0171] Examples of the sulfonium cation represented by formula (c4) include, but are not limited to, those shown below. [ka]

[0172] [ka]

[0173] [ka]

[0174] [ka]

[0175] [ka]

[0176] [ka]

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [ka]

[0181]

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[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192] [ka]

[0193] Examples of the iodonium cation represented by formula (c5) include, but are not limited to, those shown below. [ka]

[0194] The repeating units c1 to c3 include any combination of the above-mentioned anions and cations.

[0195] The base polymer may further include a repeating unit having a structure in which a hydroxy group is protected by an acid labile group (hereinafter, also referred to as repeating unit d). The repeating unit d is not particularly limited as long as it has one or more structures in which a hydroxy group is protected, and the protecting group is decomposed by the action of an acid to generate a hydroxy group, but is preferably represented by the following formula (d1). [ka]

[0196] In formula (d1), R A is the same as above. e is an integer of 1 to 4. R 41 R is a (e+1)-valent hydrocarbon group having 1 to 30 carbon atoms which may contain a heteroatom. 42 is an acid labile group.

[0197] In formula (d1), R 42 The acid labile group represented by the formula (I) may be any group that can be deprotected by the action of an acid to generate a hydroxy group. 42Although the structure is not particularly limited, an acetal structure, a ketal structure, an alkoxycarbonyl group, an alkoxymethyl group represented by the following formula (d2), and the like are preferred, and an alkoxymethyl group represented by the following formula (d2) is particularly preferred. [ka] (In the formula, * represents a bond. 43 is a hydrocarbyl group having 1 to 15 carbon atoms.

[0198] R 42 Specific examples of the acid labile group represented by the formula (d2), the alkoxymethyl group represented by the formula (d3), and the repeating unit d are the same as those exemplified in the description of the repeating unit d described in JP-A-2020-111564.

[0199] The base polymer may further contain other repeating units than those described above. For example, substituted acrylic esters such as methyl methacrylate, methyl crotonate, dimethyl maleate, and dimethyl itaconate; unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid; norbornene, norbornene derivatives, tetracyclo[6.2.1.1 3,6 .0 2,7 ] The copolymer may contain repeating units derived from cyclic olefins such as dodecene derivatives; unsaturated acid anhydrides such as itaconic anhydride; or other monomers.

[0200] The weight average molecular weight (Mw) of the base polymer is preferably 1,000 to 500,000, more preferably 3,000 to 100,000. If Mw is within this range, sufficient etching resistance is obtained, and there is no risk of a decrease in resolution due to an inability to ensure a difference in dissolution rate before and after exposure. In the present invention, Mw is a value measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0201] When the base polymer has a wide molecular weight distribution (Mw / Mn), low and high molecular weight polymers are present, which may result in foreign matter being found on the pattern or deterioration of the pattern shape after exposure. Therefore, as the pattern rule becomes finer, the effect of Mw / Mn tends to become greater, so in order to obtain a chemically amplified resist composition suitable for fine pattern dimensions, it is preferable that the Mw / Mn of the polymer has a narrow distribution of 1.0 to 2.0.

[0202] To synthesize the base polymer, for example, a monomer that provides the repeating unit described above may be polymerized in an organic solvent by heating with the addition of a radical polymerization initiator.

[0203] An example of a method for synthesizing the base polymer is a method in which one or more monomers having an unsaturated bond are polymerized by adding a radical initiator in an organic solvent and heating. Examples of organic solvents used in the polymerization reaction include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ethene (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these initiators added is preferably 0.01 to 25 mol% based on the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150° C., more preferably 60 to 100° C. The reaction time is preferably 2 to 24 hours, more preferably 2 to 12 hours from the viewpoint of production efficiency.

[0204] The polymerization initiator may be added to the monomer solution and then fed to the reaction vessel, or an initiator solution may be prepared separately from the monomer solution and then fed to the reaction vessel independently. Since there is a possibility that the polymerization reaction proceeds due to radicals generated from the initiator during the waiting time, resulting in the formation of a super-polymer, it is preferable to prepare the monomer solution and the initiator solution independently and dropwise feed them from the viewpoint of quality control. The acid labile group introduced into the monomer may be used as is, or may be protected or partially protected after polymerization. In addition, a known chain transfer agent such as dodecyl mercaptan or 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of these chain transfer agents added is preferably 0.01 to 20 mol% based on the total amount of monomers to be polymerized.

[0205] When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, hydroxystyrene or hydroxyvinylnaphthalene may be polymerized by heating with another monomer in an organic solvent after adding a radical polymerization initiator, or acetoxystyrene or acetoxyvinylnaphthalene may be used and, after polymerization, the acetoxy group may be deprotected by alkaline hydrolysis to give polyhydroxystyrene or hydroxypolyvinylnaphthalene.

[0206] As the base for the alkaline hydrolysis, ammonia water, triethylamine, etc. can be used. The reaction temperature is preferably −20 to 100° C., more preferably 0 to 60° C. The reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0207] The amount of each monomer in the monomer solution may be appropriately set so as to obtain the preferred content ratio of the repeating units described above.

[0208] The polymer obtained by the above-mentioned production method may be a reaction solution obtained by a polymerization reaction as a final product, or a powder obtained through a purification process such as a reprecipitation method in which a polymerization solution is added to a poor solvent to obtain a powder may be treated as a final product. However, from the viewpoint of work efficiency and quality stabilization, it is preferable to treat the polymer solution obtained by dissolving the powder obtained by the purification process in a solvent as a final product. Specific examples of the solvent to be used in this case include ketones such as 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, ketoalcohols such as diacetone alcohol (DAA), propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and propylene glycol. Examples of the solvent include ethers such as 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 mono tert-butyl ether acetate; lactones such as GBL; high-boiling alcohol solvents such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, and 1,3-butanediol; and mixed solvents thereof.

[0209] The concentration of the polymer in the polymer solution is preferably from 0.01 to 30% by mass, more preferably from 0.1 to 20% by mass.

[0210] The reaction solution or polymer solution is preferably filtered through a filter, which is effective in stabilizing the quality since it can remove foreign matter or gel that may cause defects.

[0211] The material of the filter used in the filter filtration includes fluorocarbon, cellulose, nylon, polyester, and hydrocarbon materials, but in the filtration process of the chemically amplified resist composition, a filter formed of a fluorocarbon, so-called Teflon (registered trademark), a hydrocarbon such as polyethylene or polypropylene, or nylon is preferred. The pore size of the filter can be appropriately selected according to the target cleanliness, but is preferably 100 nm or less, more preferably 20 nm or less. In addition, these filters may be used alone, or multiple filters may be used in combination. The filtration method may be to pass the solution through only once, but it is more preferable to circulate the solution and perform filtration multiple times. The filtration process can be performed in any order and number of times in the polymer production process, but it is preferable to filter the reaction solution after the polymerization reaction, the polymer solution, or both.

[0212] In the base polymer, the preferred content of each repeating unit can be, for example, within the ranges (mol %) shown below, but is not limited thereto. (I) one or more of the repeating units a1 or a2, preferably 1 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 50 mol %, (II) one or more of the repeating units b1 or b2 is preferably 40 to 99 mol %, more preferably 50 to 95 mol %, and even more preferably 50 to 90 mol %, (III) one or more repeating units selected from the repeating units c1 to c3, preferably from 0 to 30 mol %, more preferably from 0 to 20 mol %, and even more preferably from 0 to 15 mol %, (IV) One or more repeating units derived from other monomers, preferably 0 to 80 mol %, more preferably 0 to 70 mol %, and even more preferably 0 to 50 mol %.

[0213] The base polymer may be used alone or in combination with two or more different polymers having different composition ratios, Mw and / or Mw / Mn. The base polymer (B) may contain, in addition to the above polymer, a hydrogenated ring-opening metathesis polymer, and the one described in JP-A-2003-66612 can be used.

[0214] [(C) Organic solvent] The chemically amplified resist composition of the present invention may further comprise an organic solvent (C). The organic solvent of component (C) is not particularly limited as long as it is capable of dissolving the components described above 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; ketoalcohols 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 mono tert-butyl ether acetate; lactones such as GBL, and mixed solvents thereof.

[0215] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, cyclohexanone, GBL, DAA and mixed solvents thereof are preferred, as they have particularly excellent solubility for the base polymer of component (B).

[0216] In the chemically amplified resist composition of the present invention, the content of the organic solvent (C) is preferably 200 to 5,000 parts by mass, more preferably 400 to 3,500 parts by mass, relative to 80 parts by mass of the base polymer (B). The organic solvent (C) may be used alone or in combination of two or more kinds.

[0217] [(D) Photoacid generator] The chemically amplified resist composition of the present invention may contain a photoacid generator (D). The photoacid generator (D) is not particularly limited as long as it is a compound that generates an acid when irradiated with KrF excimer laser light, ArF excimer laser light, electron beam, or extreme ultraviolet light (hereinafter, these are also collectively referred to as high energy rays). Suitable photoacid generators include those represented by the following formula (2-1) or (2-2). [ka]

[0218] In formulas (2-1) and (2-2), R 101 ~R 105 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 101 , R 102 and R 103 Any two of the groups may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. The hydrocarbyl group includes R 31 ~R 35 Examples of the examples are similar to those given in the description of .

[0219] Examples of the cation of the sulfonium salt represented by formula (2-1) include the same as those exemplified as the sulfonium cation represented by formula (c4). Examples of the cation of the iodonium salt represented by formula (2-2) include the same as those exemplified as the iodonium cation represented by formula (c5).

[0220] In formulas (2-1) and (2-2), Xa -is an anion selected from the following formulas (2A) to (2D). [ka]

[0221] In formula (2A), R fa is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111 Examples of the examples are similar to those given in the description of .

[0222] The anion represented by formula (2A) is preferably one represented by the following formula (2A'). [ka]

[0223] In formula (2A'), R HF is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group.

[0224] In formula (2A'), R 111 is a hydrocarbyl group having 1 to 38 carbon atoms which may contain a heteroatom. In order to obtain high resolution in the formation of fine patterns, the hydrocarbyl group is preferably one having 6 to 30 carbon atoms.

[0225] R 111The hydrocarbyl group having 1 to 38 carbon atoms and represented by the formula (I) may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 38 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a pentadecyl group, a heptadecyl group and an icosyl group; a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-adamantylmethyl group, Examples of the alkyl group include cyclic saturated hydrocarbyl groups having 3 to 38 carbon atoms, such as a norbornyl group, a norbornylmethyl group, a tricyclodecanyl group, a tetracyclododecanyl group, a tetracyclododecanylmethyl group, and a dicyclohexylmethyl group; unsaturated aliphatic hydrocarbyl groups having 2 to 38 carbon atoms, such as an allyl group and a 3-cyclohexenyl group; aryl groups having 6 to 38 carbon atoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group; aralkyl groups having 7 to 38 carbon atoms, such as a benzyl group and a diphenylmethyl group; and groups obtained by combining these groups.

[0226] In addition, some or all of the hydrogen atoms of these groups may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and the -CH 2A part of - may be substituted with a group containing a hetero atom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of hydrocarbyl groups containing hetero atoms include tetrahydrofuryl groups, methoxymethyl groups, ethoxymethyl groups, methylthiomethyl groups, acetamidomethyl groups, trifluoroethyl groups, (2-methoxyethoxy)methyl groups, acetoxymethyl groups, 2-carboxy-1-cyclohexyl groups, 2-oxopropyl groups, 4-oxo-1-adamantyl groups, 5-hydroxy-1-adamantyl groups, 5-tert-butylcarbonyloxy-1-adamantyl groups, 4-oxatricyclo[4.2.1.0 3,7 ]nonane-5-one-2-yl group, 3-oxocyclohexyl group, and the like.

[0227] Synthesis of sulfonium salts having an anion represented by formula (2A') is described in detail in JP-A-2007-145797, JP-A-2008-106045, JP-A-2009-7327, JP-A-2009-258695, etc. In addition, sulfonium salts described in JP-A-2010-215608, JP-A-2012-41320, JP-A-2012-106986, JP-A-2012-153644, etc. are also preferably used.

[0228] Examples of the anion represented by formula (2A) include the same anions as those exemplified as the anions represented by formulae (c1-1) and (c1-2).

[0229] In formula (2B), R fb1 and R fb2 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111Examples of the hydrocarbyl group represented by the formula R include the same as those exemplified above. fb1 and R fb2 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fb1 and R fb2 are bonded to each other and the group to which they are bonded (-CF 2 -SO 2 -N - -SO 2 -CF 2 -) may form a ring, in which case, R fb1 and R fb2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0230] In formula (2C), R fc1 , R fc2 and R fc3 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111 Examples of the hydrocarbyl group represented by the formula R include the same as those exemplified above. fc1 , R fc2 and R fc3 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fc1 and R fc2 are bonded to each other and the group to which they are bonded (-CF 2 -SO 2 -C - -SO 2 -CF 2 -) may form a ring, in which case, R fc1 and R fc2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0231] In formula (2D), R fdis a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0232] The synthesis of a sulfonium salt having an anion represented by formula (2D) is described in detail in JP-A-2010-215608 and JP-A-2014-133723.

[0233] Examples of the anion represented by formula (2D) include the same anions as those exemplified as the anion represented by formula (1D) in JP 2018-197853 A.

[0234] Although the photoacid generator having the anion represented by formula (2D) does not have a fluorine atom at the α-position of the sulfo group, it has two trifluoromethyl groups at the β-position, and therefore has sufficient acidity to cleave the acid labile group in the base polymer, and can therefore be used as a photoacid generator.

[0235] As the photoacid generator (D), a compound represented by the following formula (3) is also preferred. [ka]

[0236] In formula (3), R 201 and R 202 R is each independently a hydrocarbyl group having 1 to 30 carbon atoms which may contain a heteroatom. 203 is a hydrocarbylene group having 1 to 30 carbon atoms which may contain a heteroatom. 201 , R 202 and R 203 Any two of may be bonded to each other to form a ring together with the sulfur atom to which they are attached.

[0237] R201 and R 202 The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl groups; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl and tricyclo[5.2.1.0]. 2,6 ] cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms such as decanyl group and adamantyl group; aryl groups having 6 to 30 carbon atoms such as phenyl group, methylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, isobutylphenyl group, sec-butylphenyl group, tert-butylphenyl group, naphthyl group, methylnaphthyl group, ethylnaphthyl group, n-propylnaphthyl group, isopropylnaphthyl group, n-butylnaphthyl group, isobutylnaphthyl group, sec-butylnaphthyl group, tert-butylnaphthyl group and anthracenyl group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and the -CH constituting the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom. 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0238] R 203The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkanediyl groups having 1 to 30 carbon atoms, such as a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, a dodecane-1,12-diyl group, a tridecane-1,13-diyl group, a tetradecane-1,14-diyl group, a pentadecane-1,15-diyl group, a hexadecane-1,16-diyl group, and a heptadecane-1,17-diyl group; a cyclopentanediyl group, a cyclohexanediyl group, and the like. cyclic saturated hydrocarbylene groups having 3 to 30 carbon atoms, such as xanediyl group, norbornanediyl group, and adamantanediyl group; arylene groups having 6 to 30 carbon atoms, such as phenylene group, methylphenylene group, ethylphenylene group, n-propylphenylene group, isopropylphenylene group, n-butylphenylene group, isobutylphenylene group, sec-butylphenylene group, tert-butylphenylene group, naphthylene group, methylnaphthylene group, ethylnaphthylene group, n-propylnaphthylene group, isopropylnaphthylene group, n-butylnaphthylene group, isobutylnaphthylene group, sec-butylnaphthylene group, and tert-butylnaphthylene group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom, such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and the -CH constituting the hydrocarbylene group may be substituted with a group containing a heteroatom, such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom. 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the heteroatom may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. As the heteroatom, an oxygen atom is preferable.

[0239] In formula (3), L A is a hydrocarbylene group having 1 to 20 carbon atoms which may contain a single bond, an ether bond, or a heteroatom. The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 203 Examples of the hydrocarbylene group represented by the formula (I) include the same as those exemplified above.

[0240] In formula (3), X a , X b , X c and X d are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. a , X b , X c and X d At least one of the groups is a fluorine atom or a trifluoromethyl group.

[0241] The photoacid generator represented by formula (3) is preferably one represented by the following formula (3'). [ka]

[0242] In formula (3'), L A is the same as above. X e R is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 301 , R 302 and R 303 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above. 1 and m 2 are each independently an integer of 0 to 5, 3 is an integer from 0 to 4.

[0243] Examples of the photoacid generator represented by formula (3) include the same as those exemplified as the photoacid generator represented by formula (2) in JP2017-026980A.

[0244] Among the other photoacid generators, those containing an anion represented by formula (2A') or (2D) are particularly preferred because of their small acid diffusion and excellent solubility in solvents. Also, those represented by formula (3') are particularly preferred because of their extremely small acid diffusion.

[0245] When the chemically amplified resist composition of the present invention contains a photoacid generator (D), the content is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 80 parts by mass of the base polymer (B). If the amount of the photoacid generator (D) added is within the above range, the resolution is good and there is no risk of problems with foreign matter occurring after development of the resist film or during stripping, which is preferable. The photoacid generator (D) may be used alone or in combination of two or more kinds.

[0246] [(E) Other quenchers] The chemically amplified resist composition of the present invention may contain (E) a quencher other than the amine compound represented by formula (1) (hereinafter also referred to as "other quencher"). Examples of the other quencher of component (E) include onium salts represented by the following formula (4-1) or (4-2). [ka]

[0247] In formula (4-1), R 401 represents a hydrogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom, except for those in which the hydrogen atom bonded to the carbon atom at the α-position of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group.

[0248] R 401The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl groups; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl and tricyclo[5.2.1.0]. 2,6 ] cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms, such as decanyl group and adamantyl group; aryl groups having 6 to 40 carbon atoms, such as phenyl group, naphthyl group and anthracenyl group; and groups obtained by combining these. In addition, some or all of the hydrogen atoms of the hydrocarbyl groups may be substituted with groups containing heteroatoms, such as oxygen atoms, sulfur atoms, nitrogen atoms and halogen atoms, and the -CH 2 A part of - may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and as a result, the group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0249] In formula (4-2), R 402 is a hydrogen atom or a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. 401 In addition to the specific examples of the substituents given above, examples of the substituents include fluorinated alkyl groups such as a trifluoromethyl group and a trifluoroethyl group, and fluorinated aryl groups such as a pentafluorophenyl group and a 4-trifluoromethylphenyl group.

[0250] Examples of the anion of the onium salt represented by formula (4-1) include, but are not limited to, those shown below. [ka]

[0251] [ka]

[0252] Examples of the anion of the onium salt represented by formula (4-2) include, but are not limited to, those shown below. [ka]

[0253] [ka]

[0254] In formulas (4-1) and (4-2), Mq + is an onium cation. The onium cation is preferably one represented by the following formula (4A), (4B) or (4C). [ka]

[0255] In formulas (4A) to (4C), R 411 ~R 419 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. 411 and R 412 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached, R 416 and R 417 and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. 401 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0256] Mq + Specific examples of the onium cation represented by the formula (I) include, but are not limited to, those shown below. [ka]

[0257] [ka]

[0258] [ka]

[0259] Specific examples of the onium salt represented by formula (4-1) or (4-2) include any combination of the above-mentioned anions and cations. These onium salts can be easily prepared by ion exchange reaction using known organic chemical methods. For ion exchange reaction, refer to, for example, JP-A-2007-145797.

[0260] The onium salt represented by formula (4-1) or (4-2) functions as a quencher in the chemically amplified resist composition of the present invention. This is because each counter anion of the onium salt is a conjugate base of a weak acid. The weak acid here means an acidity that cannot deprotect the acid labile group of the acid labile group-containing unit contained in the base polymer. The onium salt represented by formula (4-1) or (4-2) functions as a quencher when used in combination with an onium salt-type photoacid generator having a conjugate base of a strong acid such as a sulfonic acid whose α-position is fluorinated as a counter anion. That is, when an onium salt that generates a strong acid such as a sulfonic acid whose α-position is fluorinated and an onium salt that generates a weak acid such as a sulfonic acid or carboxylic acid that is not substituted with fluorine are mixed and used, when the strong acid generated from the photoacid generator by irradiation with high energy rays collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with a lower catalytic activity, and the acid appears to be deactivated, thereby enabling control of acid diffusion.

[0261] Here, when the photoacid generator that generates a strong acid is an onium salt, the strong acid generated by irradiation with high energy rays can be exchanged for a weak acid as described above, but on the other hand, it is considered that the weak acid generated by irradiation with high energy rays collides with the onium salt that generates the unreacted strong acid and is unlikely to undergo salt exchange. This is due to the phenomenon that the onium cation is more likely to form an ion pair with the anion of the strong acid.

[0262] When the onium salt represented by formula (4-1) or (4-2) is contained as the (E) other quencher, the content is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 80 parts by mass of the (B) base polymer. If the content of the onium salt is within the above range, the resolution is good and the sensitivity is not significantly reduced, which is preferable. The onium salt represented by formula (4-1) or (4-2) may be used alone or in combination of two or more kinds.

[0263] In addition, as another quencher of the component (E), a nitrogen-containing compound other than the component (A) can also be used. Such nitrogen-containing compounds include primary, secondary, or tertiary amine compounds described in paragraphs

[0146] to

[0164] of JP-A-2008-111103, particularly amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate ester bond. In addition, compounds in which a primary or secondary amine is protected with a carbamate group, such as the compounds described in JP-A-3790649, can also be used.

[0264] In addition, a sulfonium salt of sulfonic acid having a nitrogen-containing substituent may be used as the nitrogen-containing compound. Such a compound functions as a quencher in the unexposed area, and functions as a so-called photodegradable base in the exposed area, losing the quenching ability by neutralization with the acid generated by itself. By using a photodegradable base, the contrast between the exposed area and the unexposed area can be further enhanced. For example, JP-A-2009-109595 and JP-A-2012-46501 can be referred to for the photodegradable base.

[0265] When the component (E) contains a nitrogen-containing compound as another quencher, the content thereof is preferably 0.001 to 12 parts by mass, more preferably 0.01 to 8 parts by mass, relative to 80 parts by mass of the base polymer (B). The nitrogen-containing compound may be used alone or in combination of two or more kinds.

[0266] [(F) Surfactant] The chemically amplified resist composition of the present invention may further contain a surfactant (F). The surfactant of the component (F) is preferably a surfactant that is insoluble or poorly soluble in water and soluble in an alkaline developer, or a surfactant that is insoluble or poorly soluble in water and an alkaline developer. Examples of such surfactants include those described in JP-A-2010-215608 and JP-A-2011-16746.

[0267] Among the surfactants described in the above publication, preferred surfactants that are insoluble or poorly soluble in water and alkaline developers include FC-4430 (manufactured by 3M), Surflon (registered trademark) S-381 (manufactured by AGC Seimi Chemical Co., Ltd.), Olfine (registered trademark) E1004 (manufactured by Nissin Chemical Industry Co., Ltd.), KH-20, KH-30 (manufactured by AGC Seimi Chemical Co., Ltd.), and an oxetane ring-opening polymer represented by the following formula (surf-1): [ka]

[0268] Here, R, Rf, A, B, C, m, and n apply only to formula (surf-1), regardless of the above description. R is a divalent to tetravalent aliphatic group having 2 to 5 carbon atoms. Examples of the aliphatic group include divalent ones such as ethylene group, 1,4-butylene group, 1,2-propylene group, 2,2-dimethyl-1,3-propylene group, and 1,5-pentylene group, and examples of trivalent or tetravalent ones include the following: [ka] (In the formula, the dashed lines represent bonds and are partial structures derived from glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol, respectively.)

[0269] Among these, a 1,4-butylene group, a 2,2-dimethyl-1,3-propylene group, and the like are preferable.

[0270] Rf is a trifluoromethyl group or a pentafluoroethyl group, preferably a trifluoromethyl group. m is an integer of 0 to 3, n is an integer of 1 to 4, and the sum of n and m is the valence of R, which is an integer of 2 to 4. A is 1. B is an integer of 2 to 25, preferably an integer of 4 to 20. C is an integer of 0 to 10, preferably 0 or 1. The order of each constitutional unit in the formula (surf-1) is not specified, and they may be bonded in blocks or randomly. The production of a partially fluorinated oxetane ring-opening polymer surfactant is described in detail in the specification of U.S. Pat. No. 5,650,483.

[0271] A surfactant that is insoluble or poorly soluble in water and soluble in an alkaline developer has a function of reducing water penetration and leaching by orienting on the surface of the resist film when a resist protective film is not used in ArF immersion lithography. Therefore, it is useful for suppressing the elution of water-soluble components from the resist film and reducing damage to the exposure device, and is also useful because it is soluble during development with an alkaline aqueous solution after exposure and post-exposure bake (PEB), and is unlikely to become a foreign matter that causes defects. Such surfactants are insoluble or poorly soluble in water and soluble in an alkaline developer, and are polymer-type surfactants, also called hydrophobic resins, and are particularly preferred for their high water repellency and improved water slippage.

[0272] Such polymeric surfactants include those containing at least one repeating unit selected from those represented by any of the following formulas (5A) to (5E). [ka]

[0273] In formulas (5A) to (5E), R B is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 1 Ha-CH 2 -, -CH 2 CH 2 -, -O- or two -H separated from each other.s1 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms. s2 R is a single bond or a linear or branched hydrocarbylene group having 1 to 5 carbon atoms. s3 R are each independently a hydrogen atom, a hydrocarbyl group or a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, or an acid labile group. s3 When R is a hydrocarbyl group or a fluorinated hydrocarbyl group, an ether bond or a carbonyl group may be present between the carbon-carbon bonds. s4 is a (u+1)-valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 20 carbon atoms. u is an integer of 1 to 3. s5 each independently represents a hydrogen atom or -C(=O)-OR s7 R is a group represented by the formula: s7 R is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms. s6 is a hydrocarbyl group or a fluorinated hydrocarbyl group having 1 to 15 carbon atoms, and an ether bond or a carbonyl group may be present between the carbon-carbon bonds.

[0274] R s1 The hydrocarbyl group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an adamantyl group, a norbornyl group, etc. Among these, those having 1 to 6 carbon atoms are preferred.

[0275] R s2 The hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group and a pentylene group.

[0276] R s3 or R s6The hydrocarbyl group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include an alkyl group, an alkenyl group and an alkynyl group, with an alkyl group being preferred. s1 In addition to the examples of the hydrocarbyl group represented by the formula (I), examples of the hydrocarbyl group represented by the formula (I) include an n-undecyl group, an n-dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. s3 or R s6 Examples of the fluorinated hydrocarbyl group represented by the formula (1) include groups in which some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbyl group described above have been substituted with fluorine atoms. As described above, an ether bond or a carbonyl group may be present between these carbon-carbon bonds.

[0277] R s3 Examples of the acid labile group represented by the formula (L1) to (L4) include the groups represented by the formulas (L1) to (L4) above, tertiary hydrocarbyl groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, trialkylsilyl groups in which each alkyl group has 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms.

[0278] R s4 The (u+1)-valent hydrocarbon group or fluorinated hydrocarbon group represented by the formula (1) may be linear, branched, or cyclic, and specific examples thereof include groups obtained by further eliminating u hydrogen atoms from the above-mentioned hydrocarbyl group or fluorinated hydrocarbyl group.

[0279] R s7The fluorinated hydrocarbyl group represented by the formula (I) may be linear, branched or cyclic, and specific examples thereof include those in which some or all of the hydrogen atoms of the hydrocarbyl group have been substituted with fluorine atoms. Specific examples thereof include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3-trifluoro-1-propyl group, a 3,3,3-trifluoro-2-propyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,1 ,3,3,3-hexafluoroisopropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorohexyl)ethyl group, 2-(perfluorooctyl)ethyl group, and 2-(perfluorodecyl)ethyl group.

[0280] Examples of the repeating unit represented by any one of formulas (5A) to (5E) include, but are not limited to, those shown below. In the following formula, R B is the same as above. [ka]

[0281] [ka]

[0282] [ka]

[0283] [ka]

[0284] [ka]

[0285] The polymer surfactant may further contain other repeating units than the repeating units represented by formulae (5A) to (5E). Examples of the other repeating units include repeating units obtained from methacrylic acid and α-trifluoromethylacrylic acid derivatives. In the polymer surfactant, the content of the repeating units represented by formulae (5A) to (5E) in the total repeating units is preferably 20 mol % or more, more preferably 60 mol % or more, and even more preferably 100 mol %.

[0286] The Mw of the polymer surfactant is preferably from 1,000 to 500,000, and more preferably from 3,000 to 100,000. The Mw / Mn is preferably from 1.0 to 2.0, and more preferably from 1.0 to 1.6.

[0287] The method for synthesizing the polymeric surfactant includes a method in which a monomer containing an unsaturated bond that gives the repeating units represented by formulas (5A) to (5E) and other repeating units as necessary is heated in an organic solvent with the addition of a radical initiator to polymerize. Examples of the organic solvent used during polymerization include toluene, benzene, THF, diethyl ether, and dioxane. Examples of the polymerization initiator include AIBN, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The reaction temperature is preferably 50 to 100°C. The reaction time is preferably 4 to 24 hours. The acid labile group introduced into the monomer may be used as it is, or may be protected or partially protected after polymerization.

[0288] When synthesizing the polymeric surfactant, a known chain transfer agent such as dodecyl mercaptan or 2-mercaptoethanol may be used to adjust the molecular weight. In this case, the amount of the chain transfer agent added is preferably 0.01 to 10 mol% based on the total moles of the monomers to be polymerized.

[0289] When the chemically amplified resist composition of the present invention contains a surfactant (F), the content thereof 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 polymer (B). If the content of the surfactant (F) is 0.1 part by mass or more, the receding contact angle between the resist film surface and water is sufficiently improved, and if it is 50 parts by mass or less, the dissolution rate of the resist film surface in the developer is low, and the height of the formed fine pattern is sufficiently maintained. The surfactant (F) may be used alone or in combination of two or more kinds.

[0290] [Other ingredients] The chemically amplified resist composition of the present invention may contain, as other components, a compound that decomposes with an acid to generate an acid (acid amplifying compound), an organic acid derivative, a fluorine-substituted alcohol, a compound with Mw of 3,000 or less that changes in solubility in a developer by the action of an acid (dissolution inhibitor), and the like. As the acid amplifying compound, the compounds described in JP-A-2009-269953 or JP-A-2010-215608 can be referred to. When the acid amplifying compound is contained, the content is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, relative to 80 parts by mass of the (B) base polymer. If the content is too high, it is difficult to control acid diffusion, and degradation of resolution and pattern shape may occur. As the organic acid derivative, fluorine-substituted alcohol, and dissolution inhibitor, the compounds described in JP-A-2009-269953 or JP-A-2010-215608 can be referred to.

[0291] [Pattern formation method] The pattern forming method of the present invention includes the steps of forming a resist film on a substrate using the above-mentioned chemically amplified resist composition, exposing the resist film to KrF excimer laser light, ArF excimer laser light, EB or EUV, and developing the exposed resist film using a developer.

[0292] The substrate may be, for example, a substrate for manufacturing integrated circuits (Si, SiO 2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, etc.), or substrates for mask circuit manufacturing (Cr, CrO, CrON, MoSi 2 , SiO 2 etc.) can be used.

[0293] The resist film can be formed, for example, by applying the chemically amplified resist composition by a method such as spin coating to a film thickness of 0.05 to 2 μm, and then pre-baking this on a hot plate, preferably at 60 to 150° C. for 1 to 10 minutes, more preferably at 80 to 140° C. for 1 to 5 minutes.

[0294] When KrF excimer laser light, ArF excimer laser light, or EUV is used for exposing the resist film, a mask for forming a desired pattern is used, and the exposure amount is preferably 1 to 200 mJ / cm. 2 , more preferably 10 to 100 mJ / cm 2 When EB is used, the exposure dose is preferably 1 to 300 μC / cm 2 , either directly or through a mask for forming a desired pattern. 2 , more preferably 10 to 200 μC / cm 2 Irradiate so that

[0295] In addition to the usual exposure method, the immersion method can be used in which a liquid with a refractive index of 1.0 or more is placed between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[0296] The water-insoluble protective film is used to prevent elution from the resist film and to increase the water sliding property of the film surface, and is roughly divided into two types. One is an organic solvent stripping type that needs to be stripped before alkaline aqueous solution development by an organic solvent that does not dissolve the resist film, and the other is an alkaline aqueous solution soluble type that is soluble in an alkaline developer and removes the protective film together with removing the soluble part of the resist film. The latter is based on a polymer having a 1,1,1,3,3,3-hexafluoro-2-propanol residue that is insoluble in water and soluble in an alkaline developer, and is preferably a material dissolved in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixed solvent thereof. The above-mentioned water-insoluble and alkaline developer-soluble surfactant can also be dissolved in an alcohol-based solvent having 4 or more carbon atoms, an ether-based solvent having 8 to 12 carbon atoms, or a mixed solvent thereof.

[0297] After the exposure, PEB may be performed, for example, by heating on a hot plate at preferably 60 to 150° C. for 1 to 5 minutes, more preferably 80 to 140° C. for 1 to 3 minutes.

[0298] Development can be carried out, for example, using a developer of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH) of preferably 0.1 to 5 mass %, more preferably 2 to 3 mass %, for preferably 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, by a conventional method such as a dip method, a puddle method, a spray method, etc. The exposed area dissolves by development, and a target pattern is formed on the substrate.

[0299] As a means for forming a pattern, after forming a resist film, a pure water rinse (post soak) may be performed to extract an acid generator and the like from the film surface or to wash away particles, or a rinse (post soak) may be performed to remove water remaining on the film after exposure.

[0300] Furthermore, the pattern may be formed by a double patterning method. Examples of the double patterning method include a trench method in which a 1:3 trench pattern is processed by a first exposure and etching, and a 1:3 trench pattern is formed by a second exposure with a shifted position to form a 1:1 pattern, and a line method in which a first base with a 1:3 isolated leave pattern is processed by a first exposure and etching, and a second base with a 1:3 isolated leave pattern formed under the first base is processed by a second exposure with a shifted position to form a 1:1 pattern with half the pitch.

[0301] In the pattern forming method of the present invention, negative tone development can also be carried out by using an organic solvent as the developer instead of the alkaline aqueous solution to dissolve the unexposed areas.

[0302] The organic solvent development may be carried out using the following developing solutions: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, propyl cyclohexanone ... Examples of the organic solvent that can be used include methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. These organic solvents may be used alone or in combination of two or more. EXAMPLES

[0303] The present invention will be specifically described below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. The apparatuses used are as follows. IR: Thermo Fisher Scientific NICOLET 6700 · 1 H-NMR: ECA-500 manufactured by JEOL Ltd.

[0304] [1] Synthesis of amine compounds [Example 1-1] Synthesis of AQ-1 (1) Synthesis of intermediate In-1 [ka]

[0305] In a nitrogen atmosphere, raw material M-1 (17.3 g) and chloroacetyl chloride (6.8 g) were dissolved in THF (90 g) in a reaction vessel. The reaction system was cooled to below 10°C, and a solution consisting of pyridine (4.6 g) and THF (10 g) was added. After the dropwise addition, the mixture was aged for 4 hours at an internal temperature of 20°C. After the aging, the reaction system was cooled, and saturated sodium bicarbonate water (20 g) was added dropwise to stop the reaction. Then, the target product was extracted with a solvent consisting of ethyl acetate (35 g) and THF (35 g) and separated. The obtained organic layer was washed twice with saturated sodium bicarbonate water (20 g) and twice with saturated saline (20 g), and the organic layer was separated. The separated organic layer was added dropwise to a mixed solvent of water (390 g) and methanol (195 g), and the target product was crystallized. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain intermediate In-1 as white crystals (yield: 21.1 g, 99%).

[0306] (2) Synthesis of AQ-1 [ka]

[0307] Under a nitrogen atmosphere, intermediate In-1 (20.8 g), sodium iodide (0.7 g) and acetone (70 g) were charged into a reaction vessel, and morpholine (5.2 g) was added dropwise at room temperature. After the dropwise addition, the mixture was aged for 24 hours while heating under reflux. After confirming the disappearance of intermediate In-1 by TLC, the reaction solution was cooled to room temperature, and the reaction was stopped with saturated sodium bicarbonate water (35 g). Then, acetone was distilled off using an evaporator. After distillation, methylene chloride (105 g) was added to extract the target product and the liquid was separated. The obtained organic layer was washed four times with water (35 g) and once with saturated saline (35 g). The organic layer was separated and concentrated, and the residue was purified using a silica gel column to obtain AQ-1 as an oil (yield 21.9 g, 85%).

[0308] The IR spectrum data of AQ-1 is shown below. The nuclear magnetic resonance spectrum ( 1 H-NMR / DMSO-d 6 ) is shown in Figure 1. IR(D-ATR): ν= 3562, 2914, 2859, 1788, 1756, 1723, 1452, 1423, 1374, 1359, 1295, 1257, 1208, 1158, 1115, 1103, 1094, 1069, 1043, 1020, 955, 931, 902, 886, 867, 849, 819, 781, 750, 725, 530 cm -1 .

[0309] [Example 1-2] Synthesis of AQ-2 [ka]

[0310] AQ-2 was synthesized in the same manner as in Example 1-1, except that the raw material M-1 was changed to raw material M-2 (yield: 23.3 g, 90%).

[0311] The IR spectrum data of AQ-2 is shown below. The nuclear magnetic resonance spectrum ( 1 H-NMR / DMSO-d 6 ) is shown in Figure 2. IR(D-ATR): ν= 3629, 2967, 2858, 1788, 1756, 1724, 1454, 1355, 1295, 1258, 1212, 1174, 1159, 1115, 1069, 1038, 1020, 939, 902, 867, 810, 751, 495, 441cm -1 .

[0312] [Example 1-3] Synthesis of AQ-3 [ka]

[0313] AQ-3 was synthesized in the same manner as in Example 1-1, except that the raw material M-1 was changed to raw material M-3 (yield: 13.7 g, 88%).

[0314] The IR spectrum data of AQ-3 is shown below. The nuclear magnetic resonance spectrum ( 1 H-NMR / DMSO-d 6 ) is shown in Figure 3. IR(D-ATR): ν= 3559, 2965, 2878, 1789, 1756, 1723, 1455, 1356, 1295, 1260, 1207, 1173, 1158, 1134, 1115, 1070, 1041, 1020, 947, 933, 902, 867, 849, 810, 764, 747, 724, 636, 492, 440 cm -1 .

[0315] [Example 1-4] Synthesis of AQ-4 [ka]

[0316] AQ-4 was synthesized (yield: 42.5 g, yield: 90%) in the same manner as in Example 1-1, except that raw material M-1 was changed to raw material M-4.

[0317] The IR spectrum data of AQ-4 is shown below. The nuclear magnetic resonance spectrum ( 1 H-NMR / DMSO-d 6 ) is shown in Figure 4. IR(D-ATR): ν= 2966, 2874, 1788, 1757, 1722, 1454, 1388, 1370, 1356, 1295, 1259, 1212, 1157, 1115, 1070, 1038, 1020, 941, 902, 867, 810, 750, 530, 495, 422 cm -1 .

[0318] [Examples 1-5] Synthesis of AQ-5 [ka]

[0319] AQ-5 was synthesized in the same manner as in Example 1-1, except that the raw material M-1 was changed to the raw material M-5 (yield: 15.7 g, 59%).

[0320] The IR spectrum data of AQ-5 is shown below. The nuclear magnetic resonance spectrum ( 1 H-NMR / DMSO-d 6 ) is shown in Figure 5. IR(D-ATR): ν= 2967, 2937, 2873, 2810, 1788, 1755, 1748, 1720, 1452, 1422, 1405, 1394, 1366, 1346, 1297, 1283, 1267, 1256, 1226, 1215, 1192, 1169, 1160, 1115, 1078, 1057, 1041, 1025, 1013, 945, 926, 908, 890, 869, 851, 837, 813, 788, 751, 733, 719, 705, 639, 497, 442 cm -1 .

[0321] [Examples 1-6 to 1-11] Synthesis of AQ-6 to AQ-11 Amine compounds AQ-6 to AQ-11 were synthesized by various organic synthesis methods. The structures of AQ-6 to AQ-11 are shown below. [ka]

[0322] [2] Synthesis of base polymer The base polymer used in the chemically amplified resist composition was synthesized by the method described below. The Mw of the resulting polymer was measured in terms of polystyrene by GPC using THF as the solvent.

[0323] [Synthesis Example 1] Synthesis of Polymer P-1 In a nitrogen atmosphere, 5.0 g of 3-hydroxy-1-adamantyl methacrylate, 14.4 g of α-methacryloxy-γ-butyrolactone, 20.8 g of 1-isopropylcyclopentyl methacrylate, 0.49 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.41 g of 2-mercaptoethanol, and 56 g of PGMEA were placed in a flask to prepare a monomer-polymerization initiator solution. 19 g of PGMEA was placed in another flask in a nitrogen atmosphere, heated to 80° C. with stirring, and then the monomer-polymerization initiator solution was dropped over 4 hours. After the dropwise addition, the temperature of the polymerization solution was kept at 80° C. and stirring was continued for 2 hours, and then cooled to room temperature. The obtained polymerization solution was dropped into 640 g of vigorously stirred methanol, and the precipitated polymer was filtered off. The resulting polymer was washed twice with 240 g of methanol, and then vacuum dried at 50° C. for 20 hours to obtain a white powdery polymer P-1 (yield: 35.3 g, 88%). When analyzed by GPC, the Mw of the polymer P-1 was 8,500 and the Mw / Mn was 1.58. [ka]

[0324] [Synthesis Examples 2 to 7] Synthesis of Polymers P-2 to P-7 Except for changing the types and mixing ratios of the monomers, polymers P-2 to P-7 were synthesized in the same manner as in Synthesis Example 1. The types and introduction ratios of the repeating units of polymers P-1 to P-7 are shown in Table 1 below.

[0325] [Table 1]

[0326] In Table 1, the repeating units are as follows. [ka]

[0327] [3] Preparation of chemically amplified resist composition [Examples 2-1 to 2-26, Comparative Examples 1-1 to 1-14] The amine compounds of the present invention (AQ-1 to AQ-11), comparative amine quenchers (AQ-A to AQ-F), base polymers (P-1 to P-7), photoacid generators (PAG-1 to PAG-3), quenchers (Q-1, Q-2) and alkali-soluble surfactant (SF-1) were dissolved in a solvent containing 0.01 mass % of surfactant A (Omnova) in the compositions shown in Tables 2 and 3 below, and the solutions were filtered through a 0.2 μm Teflon (registered trademark) filter to prepare chemically amplified resist compositions (R-1 to R-26, CR-1 to CR-14).

[0328] [Table 2]

[0329] [Table 3]

[0330] In Tables 2 and 3, the solvent, alkali-soluble surfactant SF-1, photoacid generators PAG-1 to PAG-3, and quenchers Q-1 and Q-2 are as follows. Solvent: PGMEA (propylene glycol monomethyl ether acetate) GBL (γ-butyrolactone) DAA (Diacetone Alcohol)

[0331] Alkaline-soluble surfactant SF-1: Poly(2,2,3,3,4,4,4-heptafluoro-1-isobutyl-1-butyl methacrylate)-9-(2,2,2-trifluoro-1-trifluoromethylethyloxycarbonyl)-4-oxatricyclo[4.2.1.0 3,7 ]nonane-5-on-2-yl) [ka] Mw=7,700, Mw / Mn=1.82

[0332] Photoacid generator: PAG-1~PAG-3 [ka]

[0333] Quencher: Q-1, Q-2 [ka]

[0334] Amine quenchers for comparison: AQ-A to AQ-F [ka]

[0335] Surfactant A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane-tetrahydrofuran-2,2-dimethyl-1,3-propanediol copolymer (Omnova) [ka] a:(b+b'):(c+c')=1:4-7:0.01-1 (molar ratio) Mw=1,500

[0336] [4] Evaluation of chemically amplified resist compositions: ArF lithography evaluation (1) [Examples 3-1 to 3-12, Comparative Examples 2-1 to 2-6] An antireflective film solution (ARC29A, manufactured by Nissan Chemical Co., Ltd.) was applied onto a silicon substrate and baked at 200°C for 60 seconds to prepare an antireflective film (film thickness 100 nm). Each chemically amplified resist composition (R-1 to R-12, CR-1 to R-6) was spin-coated onto the antireflective film and baked at 100°C for 60 seconds using a hot plate to prepare a resist film with a film thickness of 90 nm. This was exposed to a line and space pattern (LS pattern) with on-wafer dimensions of a line width of 40 nm and a pitch of 80 nm, while changing the exposure dose and focus (exposure dose pitch: 1 mJ / cm2) using an ArF excimer laser scanner (Nikon Corporation, NSR-S610C, NA=1.30, dipole, Cr mask). 2 The LS pattern was then subjected to immersion exposure (mask exposure time: 100 s, focus pitch: 0.025 μm) and PEB was performed for 60 seconds at the temperature shown in Table 4 after exposure. Water was used as the immersion liquid. Then, paddle development was performed for 30 seconds in a 2.38 mass % TMAH aqueous solution, rinsed with pure water, and spin-dried to obtain a positive pattern. The developed LS pattern was observed with a Hitachi High-Technologies Corporation critical dimension SEM (CG4000), and the sensitivity, exposure tolerance (EL), mask error factor (MEF), and LWR were evaluated according to the following methods. The results are shown in Table 4.

[0337] [Sensitivity evaluation] The optimal exposure dose E for obtaining an LS pattern with a line width of 40 nm and a pitch of 80 nm op (mJ / cm 2 ) was calculated and used as the sensitivity. The smaller this value, the higher the sensitivity.

[0338] [EL Rating] From the exposure amount formed within the range of ±10% (36 to 44 nm) of the 40 nm space width in the LS pattern, EL (unit: %) was calculated by the following formula. The larger this value, the better the performance. EL(%)=(|E 1-E 2 | / E op ) x 100 E 1 : Optimal exposure dose to give LS pattern with line width of 36 nm and pitch of 80 nm E 2 : Optimal exposure dose for LS pattern with line width of 44 nm and pitch of 80 nm E op : Optimal exposure dose for LS pattern with line width of 40nm and pitch of 80nm

[0339] [MEF Rating] By changing the line width of the mask while keeping the pitch fixed, op The line width of each LS pattern irradiated with 10000 uF was observed. From the change in the line width of the mask and the line width of the LS pattern, the MEF value was calculated using the following formula. The closer this value is to 1, the better the performance. MEF = (LS pattern line width / mask line width) - b b: constant

[0340] [LWR rating] E op The dimensions of the LS pattern obtained by irradiating with 10000 times the light were measured in the longitudinal direction of the lines, and the LWR was calculated as three times the standard deviation (σ) (3σ). The smaller this value, the less roughness and the more uniform the line width of the pattern obtained.

[0341] [Table 4]

[0342] The results shown in Table 4 indicate that the chemically amplified resist composition containing the amine compound of the present invention has good sensitivity and is also excellent in EL, MEF, and LWR. Therefore, it was demonstrated that the chemically amplified resist composition of the present invention is suitable as a material for ArF immersion lithography.

[0343] [5] Evaluation of chemically amplified resist compositions: ArF lithography evaluation (2) [Examples 4-1 to 4-5, Comparative Examples 3-1 to 3-2] Each chemically amplified resist composition (R-13 to R-17, CR-7 to CR-8) was spin-coated onto a substrate for a trilayer process having a 180 nm-thick spin-on carbon film ODL-180 (carbon content 80% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and a 35 nm-thick silicon-containing spin-on hard mask SHB-A941 (silicon content 43% by mass) formed thereon, and baked at 100°C for 60 seconds using a hot plate to form a resist film with a thickness of 100 nm. This was exposed to a contact hole pattern (CH pattern) with a wafer dimension of 45 nm and a pitch of 110 nm using an ArF excimer laser immersion scanner (Nikon Corporation, NSR-S610C, NA = 1.30, σ = 0.90 / 0.72, cross-pole aperture 35 degrees, azimuthally polarized illumination, 6% halftone phase shift mask, cross-pole illumination) while varying the exposure dose and focus (exposure dose pitch: 1 mJ / cm 2 After exposure, PEB was performed at the temperature shown in Table 5 for 60 seconds. Water was used as the immersion liquid. Then, paddle development was performed with n-butyl acetate for 30 seconds, rinsed with 4-methyl-2-pentanol, and spin-dried to obtain a negative pattern. The developed CH pattern was observed with a critical dimension SEM (CG4000) manufactured by Hitachi High-Tech Corporation, and the sensitivity, MEF, CDU, and depth of focus (DOF) were evaluated according to the following methods. The results are shown in Table 5.

[0344] [Sensitivity evaluation] The optimum exposure dose E for obtaining a CH pattern with a hole dimension of 45 nm and a pitch of 110 nm op (mJ / cm 2 ) was calculated and used as the sensitivity. The smaller this value, the higher the sensitivity.

[0345] [MEF Rating] While keeping the pitch fixed, the mask dimensions are changed to obtain E op We observed each CH pattern irradiated with 10 ... MEF = (CH pattern dimension / mask dimension)-b b: constant

[0346] [CDU Rating] In the sensitivity evaluation, E op The dimensions of the CH pattern obtained by irradiating with 10000 times the exposure dose were measured at 10 points (9 CH patterns per point), and the CDU was calculated as 3 times the standard deviation (σ). The smaller this value, the better the dimensional uniformity of the CH pattern.

[0347] [DOF evaluation] For the evaluation of the depth of focus, the focus range formed within the range of ±10% (40.5 to 49.5 nm) of the dimension of 45 nm in the CH pattern was obtained. The larger this value, the wider the depth of focus.

[0348] [Table 5]

[0349] The results shown in Table 5 indicate that the chemically amplified resist composition containing the amine compound of the present invention has good sensitivity and is also excellent in MEF, CDU, and DOF, demonstrating that the chemically amplified resist composition of the present invention is suitable as a material for ArF immersion lithography.

[0350] [6] EUV lithography evaluation [Examples 5-1 to 5-9, Comparative Examples 4-1 to 4-6] Each chemically amplified resist composition (R-18 to R-26, CR-9 to CR-14) was spin-coated onto a Si substrate on which a silicon-containing spin-on hard mask SHB-A940 (silicon content 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. had been formed to a thickness of 20 nm, and the substrate was pre-baked at 100°C for 60 seconds using a hot plate to produce a resist film with a thickness of 50 nm. This was exposed to an LS pattern with an on-wafer dimension of 18 nm and a pitch of 36 nm using an ASML EUV scanner NXE3300 (NA 0.33, σ 0.9 / 0.6, dipole illumination) with varying exposure dose and focus (exposure dose pitch: 1 mJ / cm 2 After exposure, PEB was performed for 60 seconds at the temperature shown in Table 6. Thereafter, paddle development was performed with a 2.38 mass% TMAH aqueous solution for 30 seconds, followed by rinsing with a surfactant-containing rinse material and spin drying to obtain a positive pattern. The developed LS pattern was observed with a Hitachi High-Technologies Corporation critical dimension SEM (CG6300), and the sensitivity, EL, LWR and DOF were evaluated according to the following methods. The results are shown in Table 6.

[0351] [Sensitivity evaluation] The optimal exposure dose E for obtaining an LS pattern with a line width of 18 nm and a pitch of 36 nm op (mJ / cm 2 ) was calculated and used as the sensitivity.

[0352] [EL Rating] From the exposure amount formed within the range of ±10% (16.2 to 19.8 nm) of the 18 nm space width in the LS pattern, EL (unit: %) was calculated by the following formula. The larger this value, the better the performance. EL(%)=(|E 1 -E 2 | / E op ) x 100 E 1 : Optimal exposure dose for LS pattern with line width of 16.2 nm and pitch of 36 nm E 2 : Optimal exposure dose to give LS pattern with line width of 19.8 nm and pitch of 36 nm E op: Optimal exposure dose to give LS pattern with line width of 18 nm and pitch of 36 nm

[0353] [LWR rating] E op The dimensions of the LS pattern obtained by irradiating with 10000 times the light were measured in the longitudinal direction of the lines, and the LWR was calculated as three times the standard deviation (σ) (3σ). The smaller this value, the less roughness and the more uniform the line width of the pattern obtained.

[0354] [DOF evaluation] For the evaluation of the depth of focus, the focus range formed within the range of ±10% (16.2 to 19.8 nm) of the dimension of 18 nm in the LS pattern was obtained. The larger this value, the wider the depth of focus.

[0355] [Table 6]

[0356] The results shown in Table 6 indicate that the chemically amplified resist composition containing the amine compound of the present invention has good sensitivity and is excellent in EL, LWR, and DOF. Therefore, it was demonstrated that the chemically amplified resist composition of the present invention is suitable as a material for EUV lithography.

Claims

1. An amine compound represented by the following formula (1): 【Chemistry 1】 (In the formula, m is 0. R N1 and R N2 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms. N1 and R N2 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and the ring may contain -O- or -S-. N1 and R N2 cannot simultaneously become a hydrogen atom. X L is a group represented by any one of the following formulas X L -0 to X L -17. 【Chemistry 2】 (In the formula, * represents a bond to L a1 and a bond to the nitrogen atom, respectively.) L a1 is a single bond, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond or a carbamate bond. Ring R R1 is a (m+2)-valent heterocyclic group having 2 to 20 carbon atoms and having a lactone structure, lactam structure, sultone structure or sultam structure, represented by any of the following formulas: 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 (In the formula, * represents a bond to a carbon atom in L a1 and —C(═O)O—, respectively.) R 1 is a hydrocarbyl group having 1 to 20 carbon atoms. R AL is an acid labile group represented by any of the following formulas: 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

2. The amine compound according to claim 1, represented by the following formula (1A): 【Chemistry 14】 (In the formula, m, L , L a1 , R R1 , R 1 and R AL is the same as above. Ring R R2 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms formed together with the nitrogen atom in the formula, and —CH 2 - may be replaced by -O- or -S-.

3. The amine compound according to claim 2, represented by the following formula (1B): 【Chemistry 15】 (In the formula, m, L , L a1 , R R1 , R R2 , R 1 and R AL is the same as above. n is an integer from 0 to 20. Ring R R3 represents the carbon atom C in the formula A and —CH 2 - may be substituted with a group containing a heteroatom. R 2 is a hydrocarbyl group having 1 to 20 carbon atoms. When n is 2 or more, 2 or more R 2 may be the same or different, and there may be two or more R 2 may be bonded to each other to form a ring structure. R 3 is a hydrocarbyl group having 1 to 20 carbon atoms.

4. A chemically amplified resist composition comprising (A) a quencher comprising the amine compound according to any one of claims 1 to 3.

5. 5. The chemically amplified resist composition according to claim 4, further comprising (B) a base polymer having a repeating unit represented by the following formula (a1) or (a2): 【Chemistry 16】 (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X 1 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-X 11 - and X 11 is an alkanediyl group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or naphthylene group. X 2 is a single bond or *-C(=O)-O-. * indicates a bond to a carbon atom in the main chain. A.L. 1 and A.L. 2 are each independently an acid labile group. R 11 is a hydrocarbyl group having 1 to 20 carbon atoms. a is an integer from 0 to 4.

6. 6. The chemically amplified resist composition according to claim 4, wherein the base polymer contains a repeating unit represented by the following formula (b1) or (b2): 【Chemistry 17】 (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. A p is a hydrogen atom, or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxy group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride (-C(=O)-O-C(=O)-). Y 1 is a single bond or *-C(=O)-O-. * represents a bond to a carbon atom in the main chain. R 12 represents a halogen atom, a cyano group, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, or a hydrocarbylcarbonyl group having 2 to 20 carbon atoms. b is an integer from 1 to 4. c is an integer from 0 to 4, provided that 1≦b+c≦5.

7. 7. The chemically amplified resist composition according to claim 4, wherein the base polymer contains a repeating unit represented by any one of the following formulas (c1) to (c3): 【Chemistry 18】 (In the formula, R A each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z 1 is a single bond or a phenylene group. Z 2 is *-C(=O)-O-Z 21 -, *-C(=O)-NH-Z 21 -or*-O-Z 21 - is. 21 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 3 is a single bond, a phenylene group, a naphthylene group, or *-C(=O)-O-Z 31 - is. 31 is an aliphatic hydrocarbylene group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond or a lactone ring, or a phenylene group or naphthylene group. Z 4 is a single bond or *-Z 41 -C(=O)-O-. Z 41 is a hydrocarbylene group having 1 to 20 carbon atoms. Z 5 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, *-C(=O)-O-Z 51 -, *-C(=O)-NH-Z 51 -or-O-Z 51 - is. 51 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. * indicates a bond to a carbon atom in the main chain. R 21 and R 22 are each independently a hydrocarbyl group having 1 to 20 carbon atoms. 21 and R 22 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. L 11 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate ester bond, a carbonate bond or a carbamate bond. Rf 1 and Rf 2 are each independently a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. Rf 3 and Rf 4 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group having 1 to 6 carbon atoms. M - is a non-nucleophilic counterion. A + is an onium cation. d is an integer from 0 to 3.

8. The chemically amplified resist composition according to any one of claims 4 to 7, further comprising (C) an organic solvent.

9. 9. The chemically amplified resist composition according to claim 4, further comprising (D) a photoacid generator.

10. 10. The chemically amplified resist composition according to claim 4, further comprising (E) a quencher other than the amine compound represented by formula (1).

11. 11. The chemically amplified resist composition according to claim 4, further comprising (F) a surfactant.

12. A pattern forming method comprising the steps of: forming a resist film on a substrate using the chemically amplified resist composition according to any one of claims 4 to 11; exposing the resist film to KrF excimer laser light, ArF excimer laser light, an electron beam or extreme ultraviolet light; and developing the exposed resist film using a developer.

13. 13. The method for forming a pattern according to claim 12, wherein an aqueous alkaline solution is used as a developer to dissolve the exposed areas and to obtain a positive pattern in which the unexposed areas do not dissolve.

14. 13. The method for forming a pattern according to claim 12, wherein an organic solvent is used as a developer to dissolve the unexposed areas and obtain a negative pattern in which the exposed areas do not dissolve.

15. The method for forming a pattern according to any one of claims 12 to 14, wherein the exposure is an immersion exposure performed by interposing a liquid having a refractive index of 1.0 or more between the resist film and a projection lens.

16. 16. The pattern forming method according to claim 15, further comprising forming a protective film on the resist film, and performing immersion exposure by placing the liquid between the protective film and a projection lens.

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