TWI749848B - Resist composition and patterning process - Google Patents

Abstract

A resist composition containing: (A) a resin containing a repeating unit having an acid-labile group and further containing at least one repeating unit having an aromatic substituent; (B) a photo-acid generator shown by a general formula (B-1); and (C) a solvent, where W₁ represents a cyclic divalent hydrocarbon group having 4 to 12 carbon atoms with a heteroatom; W₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms without a heteroatom; Rf represents a divalent organic group shown by the following general formula; and M⁺ represents an onium cation. This provides a resist composition and a patterning process of using it that show a particularly favorable mask dimension dependency and CDU in photolithography where a light source is a high-energy beam such as a KrF excimer laser beam, an electron beam, or an extreme ultraviolet ray.

Description

Resist composition and pattern forming method

The present invention relates to a resist composition and a pattern forming method.

With the increasing integration and speed of LSI, the miniaturization is also advancing rapidly. As far as the most advanced micronization technology is concerned, mass production of ArF immersion lithography by inserting liquids such as water between the projection lens and the substrate for exposure has been implemented, and multiple exposures (multiple exposures) of ArF lithography are now being implemented. Discussion on patterning, multi-patterning, extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm, etc.

Among the chemically amplified resist materials used in the above-mentioned lithography, a compound that decomposes and generates acid due to exposure (hereinafter referred to as "acid generator") is used, and by optimizing the structure of the acid generator, it is possible to suppress The acid diffuses and can form high-resolution patterns. Such acid generators have been studied, for example, those disclosed in Patent Documents 1 to 4. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2008-074843 [Patent Document 2] JP 2009-191054 [Patent Document 3] JP 2011-126869 [Patent Document 4] JP 2012-072108

[The problem to be solved by the invention]

In the case of further miniaturization, the acid generators discussed in the past are not necessarily sufficient in terms of many performances represented by the resolution and the shape of the resist pattern.

The present invention is to solve the above-mentioned problems and aims to provide a resist composition and pattern formation that exhibit good mask size dependence (mask error coefficient: MEF) and dimensional uniformity (CDU) in photolithography method. [Means to solve the problem]

式中，W₁ 表示碳數4～12之含有雜原子之環狀2價烴基。W₂ 表示碳數4～14之不含雜原子之環狀1價烴基。Rf為上述通式表示之2價有機基，A₁ 、A₂ 分別獨立地表示氫原子或三氟甲基，B₁ 、B₂ 分別獨立地表示氫原子、氟原子或三氟甲基，*表示和羰基氧基之原子鍵。m表示0～4，n表示0～1之整數。M⁺ 表示鎓陽離子。In order to solve the above-mentioned problems, the present invention provides a resist composition characterized by containing: (A) a resin containing a repeating unit having an acid-labile group, and further containing at least one repeating unit having an aromatic substituent, ( B) The photoacid generator represented by the general formula (B-1), and (C) the solvent. [化1]

In the formula, W ₁ represents a heteroatom-containing cyclic divalent hydrocarbon group having 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms that does not contain a heteroatom. Rf is a divalent organic group represented by the above general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group, * Represents the atom bond with the carbonyloxy group. m represents 0-4, and n represents an integer of 0-1. M ⁺ represents an onium cation.

If it is such a resist composition of the present invention, it exhibits good mask size dependence (mask error coefficient: MEF) and size uniformity (CDU) in photolithography.

_{In this case, W 1} in the aforementioned general formula (B-1) is preferably a cyclic divalent hydrocarbon group containing a lactone ring structure having 6 to 12 carbon atoms.

In the case of such a resist composition, when the acid is generated after exposure, the lactone ring can be arranged at a position near the sulfonic acid group to further suppress the diffusion of the acid, so that it can exhibit better mask size dependence, Uniformity of size.

_{In addition, W 2} in the aforementioned general formula (B-1) is preferably a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms and not containing heteroatoms.

In the case of such a resist composition, by disposing a highly cyclically condensed hydrocarbon group at the end, appropriate solubility can be imparted, and therefore, a more favorable mask size dependence and size uniformity can be exhibited.

*表示和羰基氧基之原子鍵。In addition, the Rf group in the aforementioned general formula (B-1) is preferably selected from the groups represented by the following formulas (Rf-1) to (Rf-6). [化2]

* Represents the atomic bond with the carbonyloxy group.

If it is such a resist composition, the solubility is improved due to the effect of the fluorine atom in Rf, and the sulfonic acid generated after exposure becomes an appropriate acid strength, so it can exhibit better mask size dependence, LWR, size uniformity.

式中，R^A 表示氫原子或甲基。R₆₁ 表示氫原子、或碳數1～10之亦可插入雜原子之直鏈狀或分支狀或環狀之烴基。R₆₂ 表示亦可插入雜原子之碳數1～8之直鏈狀或分支狀或環狀之烴基。t為1～3之整數，u為符合u≦5+2s-t之整數。s為0或1。L₁ 表示單鍵、或-C(=O)O-、-C(=O)NH-中之任一者。In addition, in the resin of the aforementioned component (A), one of the aforementioned repeating units having an aromatic substituent is preferably a repeating unit represented by the following formula (A-1). [化3]

In the formula, R ^A represents a hydrogen atom or a methyl group. R ₆₁ represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can be inserted into a heteroatom. R ₆₂ represents a linear, branched, or cyclic hydrocarbon group with 1 to 8 carbon atoms that can be inserted into a heteroatom. t is an integer from 1 to 3, and u is an integer conforming to u≦5+2s-t. s is 0 or 1. L ₁ represents a single bond, or any one of -C(=O)O- and -C(=O)NH-.

The resist composition of the present invention can exhibit better mask size dependence or size uniformity by combining such (A) component and the above (B) component.

式中，R^A 分別獨立地為氫原子或甲基，R²⁰¹ 為單鍵、伸苯基、-O-R²¹⁰ -、或-C(=O)-Z² -R²¹⁰ -。Z² 為氧原子或NH，R²¹⁰ 為碳數1～6之直鏈狀或分支狀或環狀之伸烷基、伸烯基或伸苯基，且亦可含有羰基(-CO-)、酯基(-COO-)、醚基(-O-)或羥基。L₂ 表示單鍵、或-Z³ -C(=O)-O-，Z³ 表示碳數1～20之亦可經雜原子取代之直鏈狀或分支狀或環狀之2價烴基。Z¹ 為單鍵、亞甲基、伸乙基、伸苯基、經氟化之伸苯基、-O-R²¹¹ -、或-C(=O)-Z⁴ -R²¹¹ -。Z⁴ 為氧原子或NH，R²¹¹ 為碳數1～6之直鏈狀或分支狀或環狀之伸烷基、伸烯基或伸苯基，且亦可含有羰基、酯基、醚基或羥基。M^- 表示非親核性相對離子。R²⁰² 、R²⁰³ 、R²⁰⁴ 、R²⁰⁵ 、R²⁰⁶ 、R²⁰⁷ 、R²⁰⁸ 、R²⁰⁹ 分別獨立地表示亦可經雜原子取代、亦可插入雜原子之碳數1～20之直鏈狀、或碳數3～20之分支狀或環狀之1價烴基。又，R²⁰² 和R²⁰³ 也可相互鍵結並和式中之硫原子一起形成環，或R²⁰⁴ 、R²⁰⁵ 及R²⁰⁶ 中之任2個以上、或R²⁰⁷ 、R²⁰⁸ 及R²⁰⁹ 中之任2個以上也可相互鍵結並和式中之硫原子一起形成環。惟，前述通式(A-2)～(A-4)表示之重複單元具有1個以上之芳香族取代基。In the resin of the aforementioned component (A), one of the aforementioned repeating units having an aromatic substituent is preferably a repeating unit represented by the following general formulas (A-2) to (A-4). [化4]

In the formula, R ^{A is} each independently a hydrogen atom or a methyl group, and R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ -, or -C(=O)-Z ² -R ²¹⁰ -. Z ² is an oxygen atom or NH, R ²¹⁰ is a linear or branched or cyclic alkylene group, alkenylene group or phenylene group with 1 to 6 carbon atoms, and may also contain a carbonyl group (-CO-), Ester group (-COO-), ether group (-O-) or hydroxyl group. L ₂ represents a single bond or -Z ³ -C(=O)-O-, and Z ³ represents a linear, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that may be substituted with a heteroatom. Z ¹ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OR ²¹¹ -, or -C(=O)-Z ⁴ -R ²¹¹ -. Z ⁴ is an oxygen atom or NH, R ²¹¹ is a linear or branched or cyclic alkylene group, alkenylene group or phenylene group with 1 to 6 carbon atoms, and may also contain a carbonyl group, an ester group, and an ether group Or hydroxyl. M ^- represents a non-nucleophilic relative ion. R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ each independently represent a linear chain with 1 to 20 carbon atoms that may be substituted by heteroatoms, or may be inserted into heteroatoms. Or a branched or cyclic monovalent hydrocarbon group with 3 to 20 carbons. In addition, R ²⁰² and R ²⁰³ may also be bonded to each other and form a ring together with the sulfur atom in the formula, or any two or more of ^{R 204} , R ²⁰⁵ and R ^{206 , or one of R 207} , R ²⁰⁸ and R ²⁰⁹ Any two or more can also be bonded to each other and form a ring together with the sulfur atom in the formula. However, the repeating units represented by the aforementioned general formulas (A-2) to (A-4) have one or more aromatic substituents.

By using such component (A), the resist composition of the present invention can exhibit better mask size dependence or size uniformity.

式中，R^A 分別獨立地為氫原子或甲基。R₅₁ 及R₅₂ 分別獨立地為氫原子、或直鏈狀或分支狀或環狀之碳數1～10之1價烴基。R₅₃ 為單鍵、或直鏈狀或分支狀之碳數1～5之2價烴基。R₅₄ 、R₅₅ 及R₅₆ 分別獨立地為氫原子、或直鏈狀或分支狀或環狀之碳數1～15之1價烴基、氟化1價烴基或醯基、或酸不穩定基。R₅₄ 、R₅₅ 及R₅₆ 為1價烴基或氟化1價烴基時，它們的一部分碳原子也可經醚基或羰基取代。R₅₇ 為直鏈狀或分支狀或環狀之碳數1～20之(v+1)價之烴基或氟化烴基。v為1～3之整數。The above-mentioned resist composition preferably further contains component (D), which is a resin different from the resin of component (A), and is selected from the following formulas (D-1), (D-2) and (D-3) It is a fluorine-containing resin of at least one of the repeating units shown. [化5]

In the formula, R ^{A is} each independently a hydrogen atom or a methyl group. R ₅₁ and R ₅₂ are each independently a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₅₃ is a single bond, or a linear or branched divalent hydrocarbon group with 1 to 5 carbon atoms. R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group with 1 to 15 carbons, a fluorinated monovalent hydrocarbon group or an acyl group, or an acid labile group . When R ₅₄ , R ₅₅ and R ₅₆ are monovalent hydrocarbon groups or fluorinated monovalent hydrocarbon groups, some of their carbon atoms may be substituted with ether groups or carbonyl groups. R ₅₇ is a linear, branched, or cyclic (v+1) hydrocarbon group or fluorinated hydrocarbon group having 1 to 20 carbon atoms. v is an integer of 1-3.

The resist composition of the present invention further contains such component (D), which can improve the contact angle between the surface of the resist film and water, and suppress defects caused by residual infiltration water, or the elution of acid generators and quenchers . In addition, the solubility of the surface of the resist film can be adjusted, and good dimensional uniformity can be achieved.

In addition, the present invention provides a pattern forming method characterized by including the following steps: coating the above-mentioned resist composition on a substrate and performing heat treatment to form a resist film, exposing the above-mentioned resist film with high-energy rays, and Use developer to develop the exposed resist film.

If it is such a pattern formation method, good mask size dependence and size uniformity can be achieved in photolithography.

In the pattern forming method of the present invention, the aforementioned high-energy radiation may be an ArF excimer laser with a wavelength of 193 nm or a KrF excimer laser with a wavelength of 248 nm. In addition, the aforementioned exposure may be an immersion exposure in which a liquid with a refractive index of 1.0 or higher is inserted between the resist film and the projection lens, or a protective film may be further formed on the resist film, and the liquid It is inserted between the protective film and the projection lens to perform immersion exposure for pattern formation.

If it is such a pattern formation method, it is possible to achieve better mask size dependence and size uniformity in photolithography.

Furthermore, in the pattern forming method of the present invention, the high-energy rays may also be electron beams or extreme ultraviolet rays with a wavelength of 3-15 nm.

If it is such a pattern forming method, it is possible to form a pattern with good sensitivity and excellent MEF and CDU. [Effects of the invention]

The resist composition of the present invention can form a resist pattern particularly excellent in mask size dependence (mask error coefficient: MEF) and LWR. The present invention can provide excellent mask size dependence (mask error coefficient: MEF) and size uniformity ( CDU) resist composition and pattern formation method.

As described above, when further miniaturization, the acid generators discussed in the past are not necessarily sufficient in terms of many performances represented by resolution and resist pattern shape.

In order to achieve the above-mentioned object, the inventors of the present invention have conducted in-depth investigations and obtained the following knowledge: a resist composition using an acid generator represented by the following formula (B-1) exhibits good mask size dependence (mask error Coefficient: MEF), dimensional uniformity (CDU), extremely effective for precise micro processing.

式中，W₁ 表示碳數4～12之含有雜原子之環狀2價烴基。W₂ 表示碳數4～14之不含雜原子之環狀1價烴基。Rf為上述通式表示之2價有機基，A₁ 、A₂ 分別獨立地表示氫原子或三氟甲基，B₁ 、B₂ 分別獨立地表示氫原子、氟原子或三氟甲基，*表示和羰基氧基之原子鍵。m表示0～4，n表示0～1之整數。M⁺ 表示鎓陽離子。That is, the present invention is a resist composition characterized by containing: (A) a resin containing a repeating unit having an acid labile group, and further containing at least one repeating unit having an aromatic substituent, (B) The photoacid generator represented by the general formula (B-1), and (C) the solvent. [化6]

In the formula, W ₁ represents a heteroatom-containing cyclic divalent hydrocarbon group having 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms that does not contain a heteroatom. Rf is a divalent organic group represented by the above general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group, * Represents the atom bond with the carbonyloxy group. m represents 0-4, and n represents an integer of 0-1. M ⁺ represents an onium cation.

Hereinafter, the present invention will be described in detail, but the present invention is not limited to this. In addition, in the following chemical formulas, enantiomers or diastereomers may often exist in the chemical structure. However, as long as there is no special record, each chemical formula shall represent these stereotypes in either case. All isomers. In addition, these stereoisomers can be used singly or as a mixture.

[Resist composition] The resist composition of the present invention contains: (A) a resin (base resin) containing a repeating unit with an acid-labile group, and further containing at least one repeating unit with an aromatic substituent, (B) a general formula (B) -1) The photoacid generator and (C) solvent indicated. It can also contain specific fluorine-containing resins that are different from the resins of the (D) component and the (A) component, or other components such as quenchers, surfactants, etc., as required. Hereinafter, each component will be described.

[(A) Basic resin] In the resist composition of the present invention, the base resin (resin A) of the component (A) is a resin containing a repeating unit having an acid-labile group and at least one repeating unit having an aromatic substituent.

式中，R^A 表示氫原子或甲基。R₆₁ 表示氫原子、或碳數1～10之亦可插入雜原子之直鏈狀或分支狀或環狀之烴基。R₆₂ 表示亦可插入雜原子之碳數1～8之直鏈狀或分支狀或環狀之烴基。t為1～3之整數，u為符合u≦5+2s-t之整數。s為0或1。L₁ 表示單鍵、或-C(=O)O-、-C(=O)NH-中之任一者。(A) In the base resin of the component, the repeating unit having an aromatic substituent includes the following general formula (A-1). [化7]

In the formula, R ^A represents a hydrogen atom or a methyl group. R ₆₁ represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can be inserted into a heteroatom. R ₆₂ represents a linear, branched, or cyclic hydrocarbon group with 1 to 8 carbon atoms that can be inserted into a heteroatom. t is an integer from 1 to 3, and u is an integer conforming to u≦5+2s-t. s is 0 or 1. L ₁ represents a single bond, or any one of -C(=O)O- and -C(=O)NH-.

In the above formula, R ₆₁ represents a linear, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, which can also insert heteroatoms. Examples include methyl, ethyl, and propyl. , Isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, 1-methylcyclopentyl, 1-methyl ring Hexyl, etc., but not limited to this.

在此，破折線表示原子鍵(以下皆同)。In the above formula, R ₆₂ represents a linear, branched, or cyclic hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, which can also insert heteroatoms, except for methyl, ethyl, and propyl. In addition to, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, and cyclohexyl, the following can also be specifically exemplified, but not limited to this. [化8]

Here, dashed lines indicate atomic bonds (the same applies hereinafter).

式中，R^A 和上述同樣。Specific examples of the repeating unit represented by the aforementioned general formula (A-1) include the following, but are not limited thereto. [化9]

In the formula, R ^{A is} the same as above.

式中，R^A 和上述同樣。[化10]

In the formula, R ^{A is} the same as above.

[化11]

式中，R^A 分別獨立地為氫原子或甲基，R²⁰¹ 為單鍵、伸苯基、-O-R²¹⁰ -、或-C(=O)-Z² -R²¹⁰ -。Z² 為氧原子或NH，R²¹⁰ 為碳數1～6之直鏈狀或分支狀或環狀之伸烷基、伸烯基或伸苯基，且亦可含有羰基(-CO-)、酯基(-COO-)、醚基(-O-)或羥基。L₂ 表示單鍵、或-Z³ -C(=O)-O-，Z³ 表示碳數1～20之亦可經雜原子取代之直鏈狀或分支狀或環狀之2價烴基。Z¹ 為單鍵、亞甲基、伸乙基、伸苯基、經氟化之伸苯基、-O-R²¹¹ -、或-C(=O)-Z⁴ -R²¹¹ -。Z⁴ 為氧原子或NH，R²¹¹ 為碳數1～6之直鏈狀或分支狀或環狀之伸烷基、伸烯基或伸苯基，且亦可含有羰基、酯基、醚基或羥基。M^- 表示非親核性相對離子。M^- 可列舉：氫氧根離子、羧酸根離子、鹵素離子、硝酸根離子、亞硝酸根離子、氯酸根離子、溴酸根離子、甲磺酸根離子、對甲苯磺酸根離子、單甲基硫酸根離子、碳酸根離子、硫酸根離子等。R²⁰² 、R²⁰³ 、R²⁰⁴ 、R²⁰⁵ 、R²⁰⁶ 、R²⁰⁷ 、R²⁰⁸ 、R²⁰⁹ 分別獨立地表示亦可經雜原子取代、亦可插入雜原子之碳數1～20之直鏈狀、或碳數3～20之分支狀或環狀之1價烴基。具體可列舉：甲基、乙基、正丙基、異丙基、正丁基、三級丁基、環丙基、環戊基、環己基、環丙基甲基、4-甲基環己基、環己基甲基、降莰基、金剛烷基等烷基；乙烯基、烯丙基、丙烯基、丁烯基、己烯基、環己烯基等烯基；苯基、萘基、噻吩基等芳基；苄基、1-苯基乙基、2-苯基乙基等芳烷基等，宜為芳基。又，這些基的一部分之氫原子也可被取代為氧原子、硫原子、氮原子、鹵素原子等雜原子，也可插入氧原子、硫原子、氮原子等雜原子，其結果為也可形成或插入羥基、氰基、羰基、醚鍵、酯鍵、磺酸酯鍵、碳酸酯鍵、內酯環、磺內酯環、羧酸酐、鹵烷基等。又，R²⁰² 和R²⁰³ 也可相互鍵結並和式中之硫原子一起形成環，或R²⁰⁴ 、R²⁰⁵ 及R²⁰⁶ 中之任2個以上、或R²⁰⁷ 、R²⁰⁸ 及R²⁰⁹ 中之任2個以上也可相互鍵結並和式中之硫原子一起形成環。惟，前述通式(A-2)～(A-4)表示之重複單元具有1個以上之芳香族取代基。In the base resin of the component (A), the repeating unit having an aromatic substituent includes the following general formulas (A-2) to (A-4). [化12]

In the formula, R ^{A is} each independently a hydrogen atom or a methyl group, and R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ -, or -C(=O)-Z ² -R ²¹⁰ -. Z ² is an oxygen atom or NH, R ²¹⁰ is a linear or branched or cyclic alkylene group, alkenylene group or phenylene group with 1 to 6 carbon atoms, and may also contain a carbonyl group (-CO-), Ester group (-COO-), ether group (-O-) or hydroxyl group. L ₂ represents a single bond or -Z ³ -C(=O)-O-, and Z ³ represents a linear, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbon atoms that may be substituted with a heteroatom. Z ¹ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OR ²¹¹ -, or -C(=O)-Z ⁴ -R ²¹¹ -. Z ⁴ is an oxygen atom or NH, R ²¹¹ is a linear or branched or cyclic alkylene group, alkenylene group or phenylene group with 1 to 6 carbon atoms, and may also contain a carbonyl group, an ester group, and an ether group Or hydroxyl. M ^- represents a non-nucleophilic relative ion. M ^-can enumerate: hydroxide ion, carboxylate ion, halide ion, nitrate ion, nitrite ion, chlorate ion, bromate ion, methanesulfonate ion, p-toluenesulfonate ion, monomethyl sulfate ion Ion, carbonate ion, sulfate ion, etc. R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ each independently represent a linear chain with 1 to 20 carbon atoms that may be substituted by heteroatoms, or may be inserted into heteroatoms. Or a branched or cyclic monovalent hydrocarbon group with 3 to 20 carbons. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl , Cyclohexylmethyl, norbornyl, adamantyl and other alkyl groups; vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl and other alkenyl groups; phenyl, naphthyl, thiophene Aryl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, etc. are preferably aryl groups. In addition, the hydrogen atoms of a part of these groups may be substituted with heteroatoms such as oxygen, sulfur, nitrogen, halogen atoms, and heteroatoms such as oxygen, sulfur, and nitrogen may be inserted. As a result, it may also be formed Or insert a hydroxyl group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride, a haloalkyl group, etc. In addition, R ²⁰² and R ²⁰³ may also be bonded to each other and form a ring together with the sulfur atom in the formula, or any two or more of ^{R 204} , R ²⁰⁵ and R ^{206 , or one of R 207} , R ²⁰⁸ and R ²⁰⁹ Any two or more can also be bonded to each other and form a ring together with the sulfur atom in the formula. However, the repeating units represented by the aforementioned general formulas (A-2) to (A-4) have one or more aromatic substituents.

式中，破折線表示原子鍵。In the above formula, when L ₂ is -Z ³ -C(=O)-O-, Z ³ represents a linear, branched, or cyclic divalent with 1 to 20 carbon atoms that can be substituted by heteroatoms Specific examples of the hydrocarbon group are as follows, but are not limited thereto. [化13]

In the formula, dashed lines indicate atomic bonds.

式中，R²¹² 表示和例示作為R²⁰¹ 或例示作為上述R²⁰² 、R²⁰³ 、R²⁰⁴ 、R²⁰⁵ 、R²⁰⁶ 、R²⁰⁷ 、R²⁰⁸ 、R²⁰⁹ 之基相同者。In the above formula, R ²⁰² and R ²⁰³ may also be bonded to each other and form a ring together with the sulfur atom in the formula, or any two or more of ^{R 204} , R ²⁰⁵ and R ^{206 , or R 207} , R ²⁰⁸ and R ²⁰⁹ Any two or more of them may be bonded to each other and form a ring together with the sulfur atom in the formula. In this case, the group represented by the following formula and the like can be mentioned. [化14]

In the formula, R ²¹² represents and exemplified as R ²⁰¹ or exemplified as the same group as the above-mentioned R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ .

The specific structure of the alium cation shown in the above general formulas (A-3) to (A-4) can be exemplified below. However, the present invention is not limited to this. [化15]

式中，R¹ 為氫原子或甲基。X表示酸不穩定基。In the base resin of the component (A), the repeating unit having an acid-labile group can be exemplified by the following general formula (a1). [化16]

In the formula, R ¹ is a hydrogen atom or a methyl group. X represents an acid labile group.

The repeating unit represented by the above general formula (a1) can provide a polymer that is decomposed by the action of an acid to generate a carboxylic acid and become an alkali-soluble polymer. Various groups can be used as the acid-labile group X. Specific examples include groups represented by the following general formulas (L1) to (L9), tertiary alkyl groups having 4 to 20, preferably 4 to 15 carbon atoms, and various alkyl groups. They are trialkylsilyl groups having 1 to 6 carbon atoms, pendant oxyalkyl groups having 4 to 20 carbon atoms, and the like. [化17]

In the formula (L1), R ^L01 and R ^L02 represent a hydrogen atom or a linear or branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10, and specific examples include methyl, ethyl, Propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl, norbornyl, tricyclodecyl, tetracyclodecyl Dialkyl, adamantyl, etc. R ^L03 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 10, which may also have heteroatoms such as oxygen atoms. Examples include linear, branched, or cyclic alkyl groups, and a part of hydrogen atoms is What is substituted with a hydroxyl group, an alkoxy group, a pendant oxy group, an amino group, an alkylamino group, etc., specifically, the following substituted alkyl group etc. can be illustrated.

[化18]

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 can also be bonded to each other and form a ring with the carbon atom and oxygen atom to which they are bonded. When forming a ring, R ^L01 , R ^L02 , R ^L03 Each represents a linear or branched alkylene having 1 to 18 carbon atoms, preferably 1 to 10.

In formula (L2), R ^L04 represents a tertiary alkyl group with 4-20 carbons, ideally 4-15, and each alkyl group is a trialkylsilyl group with 1-6 carbons, and a trialkylsilyl group with 4-20 carbons. Pendant oxyalkyl groups, or groups represented by the above general formula (L1), for tertiary alkyl groups, specific examples include: tertiary butyl, tertiary pentyl, 1,1-diethylpropyl, 2 -Cyclopentylpropane-2-yl, 2-cyclohexylpropane-2-yl, 2-(bicyclo[2.2.1]heptane-2-yl)propane-2-yl, 2-(adamantane-1- Base) propan-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, etc. For trialkylsilyl, specific examples include: trimethyl Cyclohexyl group, triethylsilyl group, dimethyl-tertiary butylsilyl group, etc. For pendant oxyalkyl groups, specific examples include 3-side oxycyclohexyl, 4-methyl-2- Pendant oxolan-4-yl, 5-methyl-2-oxolan-5-yl and the like. l is an integer from 0 to 6.

In the formula (L3), R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 8 carbons and optionally substituted, or an aryl group having 6 to 20 carbons and optionally substituted, or Specific examples of substituted alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, tertiary pentyl, n-pentyl, and n-hexyl. , Cyclopentyl, cyclohexyl and other linear or branched or cyclic alkyl groups, part of their hydrogen atoms are substituted with hydroxyl, alkoxy, carboxy, alkoxycarbonyl, pendant oxy, amino, Alkylamino group, cyano group, mercapto group, alkylthio group, sulfo group, etc., as for the aryl group that may be substituted, specific examples include phenyl, methylphenyl, naphthyl, anthracene Base, phenanthrene, pyrene base, etc. In formula (L3), m is 0 or 1, n is any of 0, 1, 2, and 3, and is a number that satisfies 2m+n=2 or 3.

In the formula (L4), R ^L06 represents a linear, branched, or cyclic alkyl group having 1 to 8 carbons and optionally substituted, or an aryl group having 6 to 20 carbons and optionally substituted, and specific examples can be given. Same as R ^{L05, etc.} R ^L07 to R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group with 1 to 15 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, and tertiary Butyl, tertiary pentyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentyl methyl, cyclopentyl ethyl, cyclopentyl butyl Straight-chain or branched or cyclic alkyl groups such as cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, etc., and part of their hydrogen atoms are substituted with hydroxyl, alkoxy, carboxy, or alkoxy Carbonyl group, pendant oxy group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, sulfo group, etc. R ^L07 to R ^L16 can also be bonded to each other to form a ring (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14 Etc.) In this case, it means a divalent hydrocarbon group having 1 to 15 carbon atoms, and specifically, one obtained by removing one hydrogen atom from the monovalent hydrocarbon group exemplified above can be exemplified. In addition, the ^{adjacent carbons in R L07} to R ^L16 can be bonded to each other without any substance and form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15, etc.) .

In the formula (L5), R ^L17 , R ^L18 , and R ^L19 each independently represent a linear or branched or cyclic alkyl group having 1 to 15 carbon atoms. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1- Adamantyl, 2-adamantyl, etc.

In the formula (L6), R ^L20 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbons and optionally substituted, or an aryl group having 6 to 20 carbons and optionally substituted, and specific examples can be given. Same as R ^{L05, etc.}

In the formula (L7), R ^L21 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbons and optionally substituted, or an aryl group having 6 to 20 carbons and optionally substituted, and specific examples can be given. Same as R ^{L05, etc.} R ^L24 represents a divalent group forming a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L22 and R ^L23 each independently represent a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L22 and R ^L23 may also be bonded to each other and form a ring together with the carbon atom to which they are bonded. In this case, it represents a divalent group forming a substituted or unsubstituted cyclopentane ring or cyclohexane ring. p represents 1 or 2.

In the formula (L8), R ^L25 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, which may also be substituted, or an aryl group having 6 to 20 carbon atoms, which may also be substituted, and specific examples can be given. Same as R ^{L05, etc.} R ^L28 represents a divalent group forming a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L26 and R ^L27 each independently represent a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L26 and R ^L27 may also be bonded to each other and form a ring together with the carbon atom to which they are bonded. In this case, it represents a divalent group forming a substituted or unsubstituted cyclopentane ring or a cyclohexane ring. q means 1 or 2.

In the formula (L9), R ^L29 represents a linear, branched, or cyclic alkyl group having 1 to 10 carbons and optionally substituted, or an aryl group having 6 to 20 carbons and optionally substituted, and specific examples can be given. Same as R ^{L05, etc.} R ^L32 represents a divalent group forming a substituted or unsubstituted cyclopentane ring, cyclohexane ring or norbornane ring together with the carbon atom to which it is bonded. R ^L30 and R ^L31 each independently represent a hydrogen atom or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^L30 and R ^L31 may be bonded to each other and form a ring together with the carbon atom to which they are bonded. In this case, it represents a divalent group forming a substituted or unsubstituted cyclopentane ring or cyclohexane ring.

Among the acid labile groups represented by the above formula (L1), the following groups can be specifically exemplified for linear or branched ones.

[化19]

Among the acid labile groups represented by the above formula (L1), the cyclic ones can be specifically exemplified: tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, 2-methyl Tetrahydropyran-2-yl and the like.

The acid labile group of the above formula (L2) can be specifically exemplified: tertiary butoxycarbonyl, tertiary butoxycarbonylmethyl, tertiary pentyloxycarbonyl, tertiary pentoxycarbonylmethyl, 1,1- Diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1- Ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxy Carbonylmethyl, 2-tetrahydrofuranyloxycarbonylmethyl and the like.

The acid labile group of the above formula (L3) can be specifically exemplified: 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1- N-butylcyclopentyl, 1-second-butylcyclopentyl, 1-tertiarybutylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(4-methoxy-n-butyl)cyclopentyl , 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl- 1-cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl, etc.

The acid labile group of the above formula (L4) is preferably the group represented by the following formulas (L4-1) to (L4-4). [化20]

In the aforementioned general formulas (L4-1) to (L4-4), the broken line indicates the bonding position and the bonding direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, Secondary butyl, tertiary butyl, tertiary pentyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl, etc.

In the aforementioned general formulas (L4-1) to (L4-4), there may be enantiomers and diastereomers, and the aforementioned general formulas (L4-1) to (L4-4) Represents all of these stereoisomers. These stereoisomers can be used singly or as a mixture.

For example, the aforementioned general formula (L4-3) represents a mixture of one or two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2).

[化21]

In addition, the above-mentioned general formula (L4-4) represents one or a mixture of two or more selected from the groups represented by the following general formulas (L4-4-1) to (L4-4-4).

[化22]

The above general formulas (L4-1)～(L4-4), (L4-3-1), (L4-3-2) and (L4-4-1)～(L4-4-4) also represent them The enantiomers and mixtures of enantiomers.

式中，R¹³ 表示和例示作為R^L41 之基相同者。 參照日本特開2000-336121號公報。In addition, by making (L4-1)～(L4-4), (L4-3-1), (L4-3-2) and (L4-4-1)～(L4-4-4) respectively The bonding direction is the exo side relative to the bicyclo[2.2.1]heptane ring, and high reactivity in the acid catalyst removal reaction can be achieved (refer to JP 2000-336121 A). In the production of these monomers having a tertiary exo-alkyl group having a bicyclo[2.2.1]heptane skeleton as a substituent, there may be some monomers containing the following general formulas (L4-1-endo)～(L4- 4-endo) represents the case of monomers substituted with endoalkyl groups. In order to achieve good reactivity, the exo ratio is preferably 50% or more, and the exo ratio is more preferably 80% or more. [化23]

In the formula, R ¹³ represents the same group as the one exemplified as R ^L41. Refer to Japanese Patent Laid-Open No. 2000-336121.

Specific examples of the acid-labile group of the above formula (L4) include the following groups. [化24]

In addition, the tertiary alkyl group having 4 to 20 carbons, each alkyl group is a trialkylsilyl group having 1 to 6 carbons, and the pendant oxyalkyl group having 4 to 20 carbons can be specifically exemplified and those exemplified in ^{R L04} The same ones etc.

Specific examples of the acid labile group of the above formula (L5) include tertiary butyl, tertiary pentyl, and the following groups. [化25]

Specific examples of the acid-labile group of the above formula (L6) include the following groups. [化26]

Specific examples of the acid-labile group of the above formula (L7) include the following groups. [化27]

Specific examples of the acid labile group of the above formula (L8) include the following groups. [化28]

Specific examples of the acid-labile group of the above formula (L9) include the following groups. [化29]

式中，R¹ 表示氫原子或甲基。Specific examples of the monomer represented by the aforementioned general formula (a1) include the following, but are not limited thereto. [化30]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化31]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化32]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化33]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 和上述同樣。R⁵ 及R⁶ 分別獨立地表示氫原子或羥基。Y表示具有內酯結構之取代基、或具有磺內酯結構之取代基。Z表示氫原子、或碳數1～15之氟化烴基或碳數1～15之含氟醇之取代基。In addition, in the base resin of the component (A), in addition to the unit represented by the above general formula (a1), it is preferable to use monomers represented by the following general formulas (a2) to (a4) as necessary. [化34]

In the formula, R ^{1 is} the same as above. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydroxyl group. Y represents a substituent having a lactone structure or a substituent having a sultone structure. Z represents a hydrogen atom, or a substituent of a fluorinated hydrocarbon group having 1 to 15 carbons or a fluorinated alcohol having 1 to 15 carbons.

Specific examples of the unit represented by the aforementioned general formula (a2) include the following, but are not limited thereto. [化35]

式中，R¹ 表示氫原子或甲基。The monomer represented by the aforementioned general formula (a3) can be specifically exemplified by the following, but it is not limited thereto. [化36]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化37]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化38]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

式中，R¹ 表示氫原子或甲基。[化39]

In the formula, R ¹ represents a hydrogen atom or a methyl group.

Specific examples of the repeating unit represented by the aforementioned general formula (a4) include the following, but are not limited thereto. [化40]

In the resist composition of the present invention, monomers with carbon-carbon double bonds other than the above can also be used, for example: methyl methacrylate, methyl crotonate, dimethyl maleate, dimethyl iconate Substituted acrylates such as esters; unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid; norbornene, norbornene derivatives, tetracyclic [4.4.0.1 ^2,5 .17 ^7,10 ] Cyclic olefins such as dodecene derivatives; unsaturated acid anhydrides such as itaconic anhydride, α-methylene-γ-butyrolactone, α-methylstyrene, and other monomers.

The weight average molecular weight (Mw) of the resin A (the base resin of the component (A)) is preferably 1,000 to 500,000, and more preferably 3,000 to 100,000. If it is the aforementioned range, there is no doubt that the etching resistance is reduced, or the contrast before and after exposure cannot be ensured, and the resolution is reduced. In addition, in the present invention, Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or dimethylacetamide (DMF) as a solvent.

In addition, in resin A, when the molecular weight distribution (Mw/Mn) is wide, both low-molecular-weight and high-molecular-weight polymers exist. Therefore, there is a concern that foreign matter is observed on the pattern after exposure, or the shape of the pattern deteriorates. Therefore, the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rules become finer. Therefore, in order to obtain a resist composition suitable for fine pattern sizes, the molecular weight distribution of resin A is preferably 1.0 to 2.0. The narrow dispersion of 1.0～1.5 is particularly good.

The method of synthesizing resin A includes, for example, monomers with unsaturated bonds that will be used to obtain repeating units represented by formula (a1) and repeating units represented by formulas (a2) to (a4) or other repeating units as needed. In an organic solvent, a free radical initiator is added to implement the method of heating polymerization. Examples of the organic solvent used in the polymerization include toluene, benzene, THF, diethyl ether, diethane, methyl ethyl ketone, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), and the like. The polymerization initiator can include: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis( 2-methylpropionic acid) dimethyl ester, benzyl peroxide, laurel peroxide, etc. The reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. The reaction time is preferably 2-24 hours. The acid labile group can be directly introduced into the monomer, or it can be protected or partially protected after polymerization. Furthermore, in order to adjust the molecular weight, it is also possible to perform polymerization using a known chain transfer agent such as dodecyl mercaptan and 2-mercaptoethanol. At this time, the addition amount of the chain transfer agent is preferably an amount of 0.01-10 in terms of molar ratio with respect to all monomers to be polymerized.

In resin A, the ideal content ratio of each repeating unit derived from each monomer can be set to the range shown below, for example, but it is not limited to this.

(I) The repeating unit represented by the formula (a1) preferably contains 1 to 99 mol%, more preferably 20 to 95 mol%, and even more preferably 30 to 90 mol%, which can be based on needs. (II) The repeating unit represented by formula (A-1) preferably contains 1 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 60 mol%, (III) At least one selected from the repeating units represented by formulas (A-2)～(A-4) preferably contains 1-40 mol%, more preferably 3-35 mol%, and 5-30 Mole% is even better, (IV) At least one selected from the repeating units represented by formulas (a2)～(a4) preferably contains 0-99 mol%, more preferably 0-90 mol%, and 0-70 mol%. Better, (V) Other repeating units preferably contain 0-99 mol%, more preferably 0-70 mol%, and even more preferably 0-50 mol%.

In addition, the base resin of component (A) can also contain two or more resins with different composition ratios, molecular weights or molecular weight distributions. It can also contain resins that have repeating units with acid-labile groups as needed, and also contain no A resin containing a repeating unit represented by formula (a1).

式中，W₁ 表示碳數4～12之含有雜原子之環狀2價烴基。W₂ 表示碳數4～14之不含雜原子之環狀1價烴基。Rf為上述通式表示之2價有機基，A₁ 、A₂ 分別獨立地表示氫原子或三氟甲基，B₁ 、B₂ 分別獨立地表示氫原子、氟原子或三氟甲基，*表示和羰基氧基之原子鍵。m表示0～4，n表示0～1之整數。M⁺ 表示鎓陽離子。[(B) Photo acid generator] The resist composition of the present invention contains a photo acid generator represented by the following formula (B-1) as the (B) component. [化41]

In the formula, W ₁ represents a heteroatom-containing cyclic divalent hydrocarbon group having 4 to 12 carbon atoms. W ₂ represents a cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms that does not contain a heteroatom. Rf is a divalent organic group represented by the above general formula, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, and B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group, * Represents the atom bond with the carbonyloxy group. m represents 0-4, and n represents an integer of 0-1. M ⁺ represents an onium cation.

*表示和氧基羰基之原子鍵。Specific examples of the heteroatom-containing cyclic divalent hydrocarbon group having 4 to 12 carbon atoms represented by W _{1 include the following.} [化42]

* Represents the atomic bond with the oxycarbonyl group.

Particularly preferable in terms of W ₁ include a cyclic divalent hydrocarbon group containing a lactone ring structure, and a cyclic divalent hydrocarbon group containing a lactone ring structure having 6 to 12 carbon atoms is particularly preferable. When the acid is generated after exposure, by arranging the lactone ring at a position near the sulfonic acid group, the diffusion of the acid can be more suppressed.

破折線表示原子鍵。Specific examples of the cyclic monovalent hydrocarbon group having 4 to 14 carbon atoms and not containing a heteroatom represented by W _{2 include the following.} [化43]

The dashed line represents the atomic bond.

W _{2 is} preferably a polycyclic monovalent hydrocarbon group having 7 to 14 carbon atoms without heteroatoms. As far as W _{2 is} concerned, an adamantyl group is particularly preferable. By arranging a highly condensed hydrocarbon group at the end, appropriate solubility can be imparted.

Rf is a divalent organic group represented by the above general formula. Here, A ₁ and A ₂ each independently represent a hydrogen atom or a trifluoromethyl group, B ₁ and B ₂ each independently represent a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and * represents an atomic bond with a carbonyloxy group. m represents 0-4, and n represents an integer of 0-1. It should be m+n>0.

*表示和羰基氧基之原子鍵。The Rf group is preferably selected from the group represented by the following formulas (Rf-1) to (Rf-6). [化44]

* Represents the atomic bond with the carbonyloxy group.

If the photoacid generator represented by the formula (B-1) has such Rf, the solubility is improved due to the effect of the fluorine atom, and the sulfonic acid generated after exposure becomes an appropriate acid strength, so it is preferable.

The specific example of the structure of the anion part of the photoacid generator represented by the formula (B-1) is shown below, but it is not limited thereto. [化45]

[化46]

[化47]

In the formula (B-1), ^{the onium cation represented by M +} is preferably at least one selected from the cations represented by the following formula (b1) and formula (b2). [化48]

In the formulas (b1) and (b2), R ⁴¹ to R ⁴⁵ are each independently a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms that may contain a hetero atom. In addition, ^{any two of R 41} , R ⁴² and R ⁴³ may be bonded to each other and form a ring with the sulfur atom in the formula.

The ^{monovalent hydrocarbon groups represented by R 41} to R ⁴⁵ include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, cyclopropyl, cyclopentyl, cyclohexyl, and cyclopropyl Alkyl groups such as methyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl; vinyl, allyl, propenyl, butenyl, hexenyl, cyclohexenyl and other alkenes Group; aryl groups such as phenyl, naphthyl, and thienyl; aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, etc. Among them, an aryl group is preferred. In addition, part of the hydrogen atoms of the aforementioned monovalent hydrocarbon groups may be substituted with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the carbon atoms of these groups may be substituted with oxygen atoms, Sulfur atom, nitrogen atom and other heteroatom groups, as a result, may also contain hydroxyl, cyano, carbonyl, ether, ester, sulfonate, carbonate, lactone, sultone, carboxylic anhydride , Haloalkyl, etc.

The alium cation represented by the formula (b1) can be exemplified as shown below, but is not limited thereto. [化49]

[化50]

[化51]

[化52]

[化53]

[化54]

[化55]

[化56]

The iodonium cation represented by the formula (b2) can be exemplified as follows, but is not limited thereto. [化57]

In addition, the resist composition of the present invention may further contain other photoacid generators other than the aforementioned photoacid generator in order to fine-tune the fine imaging performance. As for other photoacid generators, any compound can be used as long as it is a compound that generates an acid due to high-energy ray irradiation, and it may be a known one used in a conventional resist composition, especially a chemical amplification resist composition. As far as other ideal photoacid generators are concerned, there are sulfonium salt, iodonium salt, sulfodiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generator, etc. They can One type is used alone or two or more types are used in combination. As far as the acid produced from other photoacid generators is concerned, it is preferably a strong acid such as sulfonic acid, (bisperfluoroalkanesulfonyl) imide, (perfluoromethanesulfonyl) methide, or a strong acid such as carboxylic acid The weak acid.

Specific examples of other photoacid generators include the following formula (B-2), formula (B-3), and formula (B-4). [化58]

In the formula (B-2), A ¹ is a hydrogen atom or a trifluoromethyl group. R ²¹ is a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, or a nitrogen-containing heterocyclic group, or a group represented by the following formula (i), which may also contain an oxygen atom. M ⁺ is an onium cation. [化59]

In the formula (i), R ³¹ and R ³² are each independently a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbons which may also contain a hetero atom. R ³¹ and R ³² may also be bonded to each other and form a ring together with the nitrogen atom to which they are bonded. R ³³ is a linear, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbons that may contain heteroatoms.

The ^{monovalent hydrocarbon group represented by R 21} which may also contain an oxygen atom includes: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl , Octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, 1-adamantyl, 1-adamantylmethyl Alkyl groups; groups containing steroid structure; 2-side oxycyclopentyl, 2-side oxycyclohexyl, 4-side oxycyclohexyl, 2-side oxypropyl, 2-side oxyethyl , 2-cyclopentyl-2-side oxyethyl, 2-cyclohexyl-2-side oxyethyl, 2-(4-methylcyclohexyl)-2-side oxyethyl, 4-oxy Hetero-tricyclic [4.2.1.0 ^3,7 ] nonane-5-one-9-yl, 4-lateral oxy-1-adamantyl and other side oxyalkyl groups; phenyl, 1-naphthyl, 2 -Naphthyl, anthracenyl, thienyl, 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4- Alkoxy phenyl such as tertiary butoxyphenyl and 3-tertiary butoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylbenzene Alkyl, 4-tertiary butyl phenyl, 4-n-butyl phenyl, 2,4-dimethyl phenyl and other alkyl phenyl groups, methyl naphthyl, ethyl naphthyl and other alkyl naphthyl groups, methyl Alkoxynaphthyl such as oxynaphthyl and ethoxynaphthyl, dialkylnaphthyl such as dimethylnaphthyl and diethylnaphthyl, dimethoxynaphthyl, diethoxynaphthyl and other two Aryl groups such as alkoxynaphthyl; aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl; 2-phenyl-2-oxoethyl, 2-(1-naphthyl ) An aryl-side oxyalkyl group such as 2-aryl-2-side oxyethyl group, such as 2-sided oxyethyl group, 2-(2-naphthyl)-2-side oxyethyl group, and the like. Other examples include vinyl, isopropenyl and the like.

、咔唑、吖啶、啡𠯤、啡啶、1,10-啡啉、啡㗁𠯤、吲哚啉、異吲哚啉、𪡓啶、苯并[e]吲哚、苯并[cd]吲哚。The nitrogen-containing heterocyclic group represented by R ²¹ includes: aziridine, pyrrolidine, piperidine, pyrrolidine, pyrrole, pyridine, azetine, azole, isoazole, thiazole, isothiazole, imidazole , Pyrazole, pyrazole, pyrimidine, pyridine, pyrroline, 2-imidazoline, imidazoline, 3-pyrazoline, pyrazoline, piperidine, tripyridine, dithiazolyl, indole, Isoindole, quinoline, isoquinoline, quinoline, quinoline, quinazoline, quinoline, 1,8-pyridine, purine, pteridine, indole

, Carbazole, acridine, phenanthrene, phenanthrene, 1,10-phenanthroline, phenanthrene, indoline, isoindoline, pyridine, benzo[e]indole, benzo[cd]indole Indole.

Particularly preferred as R ²¹ include: tertiary butyl, cyclohexyl, 1-adamantyl, 1-adamantylmethyl, 4-oxa-tricyclo[4.2.1.0 ^3,7 ]nonane-5 -Keto-9-yl, 4- pendant oxy-1-adamantyl, alkyl containing steroid structure, etc.

In formula (i), ^{the monovalent hydrocarbon groups represented by R 31} and R ³² include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, and hexyl. , Heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, adamantyl and other alkyl groups; vinyl, Allyl, propenyl, butenyl, hexenyl, cyclohexenyl and other alkenyl groups; phenyl, naphthyl, thienyl and other aryl groups; benzyl, 1-phenylethyl, 2-phenylethyl Group and other aralkyl groups. In addition, in the aforementioned hydrocarbon groups, part of the hydrogen atoms may be substituted with the aforementioned monovalent hydrocarbon groups, or groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or part of the carbon atoms of these groups It is substituted with a group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, etc. As a result, it may also contain a hydroxyl group, a cyano group, a carbonyl group, an ether group, an ester group, a sulfonate group, a carbonate group, a lactone ring, Sultone ring, carboxylic anhydride, haloalkyl, etc.

、咔唑、吖啶、啡𠯤、啡啶、1,10-啡啉、啡㗁𠯤、吲哚啉、異吲哚啉、𪡓啶、苯并[e]吲哚、苯并[cd]吲哚等。又，這些環的一部分之氫原子也可被取代為前述烴基、或含有氧原子、硫原子、氮原子、鹵素原子等雜原子之基，或這些環的一部分之碳原子也可被取代為含有氧原子、硫原子、氮原子等雜原子之基，其結果為也可含有羥基、氰基、羰基、醚基、酯基、磺酸酯基、碳酸酯基、內酯環、磺內酯環、羧酸酐、鹵烷基等。When R ³¹ and R ³² are bonded to each other and form a ring together with the nitrogen atom to which they are bonded, the specific ring types can include: aziridine, pyrrolidine, piperidine, pyrroline, pyrrole, pyridine, dihydroazepine , Azole, isoazole, thiazole, isothiazole, imidazole, pyrazole, pyrimidine, pyrimidine, pyrazole, pyrroline, 2-imidazoline, imidazoline, 3-pyrazoline, pyrazoline, piperazine, Three, two, dithia, indole, isoindole, quinoline, isoquinoline, quinoline, quinoline, quinazoline, quinoline, 1,8-pyridine, purine, pteridine Ind

, Carbazole, acridine, phenanthrene, phenanthrene, 1,10-phenanthroline, phenanthrene, indoline, isoindoline, pyridine, benzo[e]indole, benzo[cd]indole Indole etc. In addition, part of the hydrogen atoms of these rings may be substituted with the aforementioned hydrocarbon groups, or groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, or part of the carbon atoms of these rings may be substituted with The group of heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, as a result, may also contain hydroxyl group, cyano group, carbonyl group, ether group, ester group, sulfonate group, carbonate group, lactone ring, sultone ring , Carboxylic anhydride, haloalkyl, etc.

In formula (i), ^{the divalent hydrocarbon group represented by R 33} includes: methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5- Diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10- Diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane -1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl and other linear alkanediyl groups; the methyl, ethyl, propyl, isopropyl , Butyl, secondary butyl, tertiary butyl and other side chains added to the aforementioned straight-chain alkanediyl to form a branched alkanediyl group; cyclopentanediyl, cyclohexanediyl, norbornane Saturated cyclic hydrocarbon groups such as diyl and adamantanediyl; unsaturated cyclic divalent hydrocarbon groups such as phenylene and naphthylene. In addition, part 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, or part of the carbon atoms of these groups may be inserted containing oxygen atoms, sulfur atoms, Heteroatom groups such as nitrogen atoms, as a result, may also contain hydroxyl groups, cyano groups, carbonyl groups, ether groups, ester groups, sulfonate groups, carbonate groups, lactone rings, sultone rings, carboxylic acid anhydrides, and alkyl halides. Base etc.

The specific example of the structure of the anion part of the photoacid generator represented by formula (B-2) is shown below, but it is not limited thereto. In addition, in the following formula, A ^{1 is the} same as described above. [化60]

[化61]

In the formula (B-2), ^{the onium cation represented by M +} is preferably at least one selected from the cations represented by the aforementioned formula (b1) and formula (b2).

In the formula (B-3), A ² is a hydrogen atom or a trifluoromethyl group. R ²² , R ^23, and R ²⁴ are each independently a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 20 carbons which may also contain a hetero atom. p and q are each independently an integer of 0-5. r is an integer of 0-4. L is a single bond, an ether group, or a linear, branched, or cyclic divalent hydrocarbon group with 1 to 20 carbons that may also contain heteroatoms.

The ^{monovalent hydrocarbon groups represented by R 22} , R ²³ and R ²⁴ include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, tertiary pentyl, and n-pentyl. Base, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexyl Alkyl groups such as methyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.0 ^2,6 ]decyl, adamantyl, etc. In addition, part 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, or part of the carbon atoms of these groups may be substituted with oxygen atoms, sulfur atoms, etc. Atoms, nitrogen atoms and other heteroatom groups, as a result, may also contain hydroxyl groups, cyano groups, carbonyl groups, ether groups, ester groups, sulfonate groups, carbonate groups, lactone rings, sultone rings, carboxylic anhydrides, Haloalkyl, etc. R ²² , R ²³ and R ^{24 are} preferably methyl, methoxy, tertiary butyl, tertiary butoxy and the like.

In the formula (B-3), the divalent hydrocarbon group represented by L may be the ^{same as the one already exemplified as R 33} , and it may also be a combination of two or more of these groups. In addition, part 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, or part of the carbon atoms of these groups may be substituted with oxygen atoms, sulfur atoms, etc. Atoms, nitrogen atoms and other heteroatom groups, as a result, may also contain hydroxyl groups, cyano groups, carbonyl groups, ether groups, ester groups, sulfonate groups, carbonate groups, lactone rings, sultone rings, carboxylic anhydrides, Haloalkyl, etc.

The photoacid generator represented by the formula (B-3) can be exemplified as shown below, but it is not limited thereto. In addition, in the following formula, A ^{2 is the} same as described above. [化62]

[化63]

(B) The photoacid generator may further contain the compound represented by the above-mentioned formula (B-4). In formula (B-4), A ³ and A ⁴ are each independently a hydrogen atom or a trifluoromethyl group, and they are not a hydrogen atom at the same time. R ²⁵ is a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 35 carbon atoms, or a nitrogen-containing heterocyclic group, or a group represented by the aforementioned formula (i), which may also contain an oxygen atom. M ^{+ is the} same as the aforementioned onium cation.

The specific example of the structure of the anion part of the photoacid generator represented by the formula (B-4) is shown below, but it is not limited thereto. [化64]

[化65]

Among the above-mentioned other photoacid generators, compounds having a fluorine atom-containing structure represented by trifluoromethyl in the anionic structure portion have high hydrophobicity and little elution into infiltrating water. In addition, since it has a structure containing fluorine atoms, it has high solvent solubility, and organic solvents can reduce residues after development during development. This can reduce defects after development and is suitable as a resist composition for ArF immersion exposure.

Specific examples other than the aforementioned photoacid generators include, for example, the compounds described in paragraphs [0122] to [0142] of JP 2008-111103 A, and particularly preferred ones include: JP 2014- The compound described in paragraphs [0088] to [0092] of 001259, the compound described in paragraphs [0015] to [0017] of JP 2012-41320, the paragraph of JP 2012-106986 [ 0015] to [0029] the compounds described in, etc. The partially fluorinated sulfonic acid generating type photoacid generator described in the aforementioned publication, especially in ArF lithography, has moderate strength and diffusion distance of the acid generated and can be used ideally.

The content of the photoacid generator of component (B) relative to 100 parts by mass of the base resin of component (A) is preferably 0.1-50 parts by mass, more preferably 0.2-40 parts by mass, and even more preferably 0.3-35 parts by mass . If it is in the aforementioned range, the resolution will not be degraded, and there will be no doubt that foreign matter will be generated when the resist film is developed or peeled off. In addition, the content when the compound represented by the formula (B-4) is added is preferably 0-50% by mass in the photoacid generator of the component (B).

[(C) Solvent] The resist composition of the present invention contains a solvent as the (C) component. Examples of the aforementioned solvent include: ketones such as cyclohexanone and methyl-2-n-pentyl ketone described in paragraphs [0144] to [0145] of JP 2008-111103 A; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and other alcohols; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, Propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, tertiary butyl acetate, tertiary butyl propionate, propylene glycol mono tertiary butyl ether acetate and other esters; γ-butyrolactone, etc. Lactones and ketone alcohols such as diacetone alcohol; its mixed solvent. When using an acetal acid-labile group, in order to accelerate the deprotection reaction of the acetal, a high-boiling alcohol solvent may be added. Specifically, diethylene glycol, propylene glycol, glycerin, 1,4- Butanediol, 1,3-butanediol, etc.

The content of the solvent of the component (C) is preferably 100 to 10,000 parts by mass, more preferably 300 to 8,000 parts by mass relative to 100 parts by mass of the base resin of the component (A).

[(D) Fluorine-containing resin] The resist composition of the present invention may also contain a resin that is different from the aforementioned resin A, and contains a resin selected from the following formulas (D-1), (D-2) and (D) -3) A fluorine-containing resin of at least one of the repeating units indicated. [化66]

In the formula, R ^A is a hydrogen atom or a methyl group. R ₅₁ and R ₅₂ are each independently a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 10 carbon atoms. R ₅₃ is a single bond, or a linear or branched divalent hydrocarbon group with 1 to 5 carbon atoms. R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group with 1 to 15 carbons, a fluorinated monovalent hydrocarbon group or an acyl group, or an acid labile group . When R ₅₄ , R ₅₅ and R ₅₆ are monovalent hydrocarbon groups or fluorinated monovalent hydrocarbon groups, some of their carbon atoms may be substituted with ether groups or carbonyl groups. R ₅₇ is a linear, branched, or cyclic (v+1) hydrocarbon group or fluorinated hydrocarbon group having 1 to 20 carbon atoms. v is an integer of 1-3.

The _{monovalent hydrocarbon groups with 1-10 carbons represented by R 51} and R ₅₂ include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, secondary butyl, Alkyl groups such as tertiary butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, adamantyl, norbornyl. Among them, a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 6 carbon atoms is preferable.

_{Specific examples of the divalent hydrocarbon group with 1 to 5 carbon atoms represented by R53} include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene and the like.

Examples of the monovalent hydrocarbon group having 1 to 15 carbon atoms represented by R ₅₄ , R ₅₅ and R ₅₆ include an alkyl group, an alkenyl group, an alkynyl group, etc., and an alkyl group is preferable. Examples of the aforementioned alkyl group include those mentioned above, and also n-undecyl group, n-dodecyl group, tridecyl group, tetradecyl group, pentadecyl group and the like. Examples of the fluorinated monovalent hydrocarbon group having 1 to 15 carbon atoms include groups in which a part or all of the hydrogen atoms bonded to the carbon atoms of the monovalent hydrocarbon group are substituted with fluorine atoms. As mentioned above, some of their carbon atoms may also be substituted with ether groups or carbonyl groups.

When R ₅₄ , R ₅₅ and R ₅₆ are acid-labile groups, specific examples include: groups represented by the aforementioned formulas (L1) to (L9), and tertiary alkyl groups having 4 to 20 carbon atoms, preferably 4 to 15 , Each alkyl group is a trialkylsilyl group with a carbon number of 1 to 6, a pendant oxyalkyl group with a carbon number of 4 to 20, etc.

Examples of the (v+1)-valent hydrocarbon group or fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R _{57 include groups obtained by removing a necessary number of hydrogen atoms from the aforementioned monovalent hydrocarbon group or fluorinated monovalent hydrocarbon group.}

The repeating unit represented by formula (D-1) can be exemplified as shown below, but it is not limited thereto. Further, in the formula, R ^A, and the same. [化67]

The repeating unit represented by formula (D-2) can be exemplified as shown below, but it is not limited thereto. Further, in the formula, R ^A, and the same. [化68]

The repeating unit represented by formula (D-3) can be exemplified as shown below, but it is not limited thereto. Further, in the formula, R ^A, and the same. [化69]

The Mw of the fluorine-containing resin of the component (D) is preferably 1,000 to 100,000, more preferably 3,000 to 15,000. Mw/Mn is preferably 1.0 to 2.0, more preferably 1.0 to 1.6.

When synthesizing the fluorine-containing resin of component (D), one method can be exemplified to obtain the repeating units represented by formulas (D-1)～(D-3) and other repeating units with unsaturated bonds as required The monomer is heated and polymerized by adding a free radical initiator in an organic solvent. Examples of organic solvents used in the polymerization include toluene, benzene, THF, diethyl ether, diethane, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. The polymerization initiator can include: AIBN, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylpropionic acid) dimethyl, peroxide Benzoyl, laurel peroxide, etc. The reaction temperature is preferably 50-100°C. The reaction time is preferably 4-24 hours. The acid labile group can be directly introduced into the monomer, or it can be protected or partially protected after polymerization. Furthermore, in order to adjust the molecular weight, it is also possible to perform polymerization using a known chain transfer agent such as dodecyl mercaptan and 2-mercaptoethanol. At this time, the addition amount of the chain transfer agent is preferably an amount of 0.01-10 in terms of molar ratio with respect to all monomers to be polymerized.

When the resist composition of the present invention contains the fluorine-containing resin of component (D), its content is preferably 0.1-50 parts by mass, more preferably 0.5-10 parts by mass relative to 100 parts by mass of the base resin of component (A). If the content is in the aforementioned range, the contact angle between the surface of the resist film and water can be sufficiently improved, and defects caused by residual infiltration water, or the elution of acid generators and quenchers can be suppressed. In addition, the solubility of the resist film surface can be adjusted to achieve good dimensional uniformity.

[Other ingredients] The resist composition of the present invention may also contain amine compounds, sulfonates or carboxylates as quenchers as required. In this specification, the quencher means a compound that can suppress the diffusion rate when the acid generated from the photoacid generator diffuses in the resist film.

Among such quenchers, amine compounds include primary, secondary, or tertiary amine compounds described in paragraphs [0146] to [0164] of JP 2008-111103 A, especially those having hydroxyl groups and ether groups. An amine compound of any one of, ester group, lactone ring, cyano group, sulfonate group, etc. is a desirable example. In addition, compounds in which primary or secondary amines are protected as urethane groups like the compounds described in Japanese Patent No. 3790649 can also be cited. Such a protected amine compound is effective when there are ingredients unstable to alkali in the resist composition.

Examples of the aforementioned sulfonate include compounds represented by the following formula (Z1). In addition, as the aforementioned carboxylate, a compound represented by the following formula (Z2) can be exemplified. [化70]

R ¹⁰¹ is a hydrogen atom or a hydrocarbon group with 1 to 40 carbon atoms which may also contain a hetero atom, but excludes the case where 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. M ^{+ is} each independently an onium cation, and the same as those exemplified above can be mentioned.

The aforementioned hydrocarbon group may be saturated or unsaturated, and may be either linear, branched, or cyclic. Specific examples include: methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, tertiary pentyl, n-pentyl, n-hexyl, n-octyl, 2 -Ethylhexyl, n-nonyl, n-decyl and other alkyl groups; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl , Cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0 ^2,6 ]decyl, adamantyl, adamantylmethyl and other cyclic saturated hydrocarbon groups; alkenyl can include vinyl, allyl, propylene Alkenyl, butenyl, hexenyl and other alkenyl groups; unsaturated aliphatic cyclic hydrocarbon groups such as cyclohexenyl; phenyl, naphthyl, alkylphenyl (2-methylphenyl, 3-methylphenyl) , 4-methylphenyl, 4-ethylphenyl, 4-tertiary butylphenyl, 4-n-butylphenyl, etc.), dialkylphenyl (2,4-dimethylphenyl, 2,4,6-Triisopropylphenyl, etc.), alkylnaphthyl (methylnaphthyl, ethylnaphthyl, etc.), dialkylnaphthyl (dimethylnaphthyl, diethylnaphthyl, etc.) ) And other aryl groups; heteroaryl groups such as thienyl group; aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, etc.

In addition, part of the hydrogen atoms of these groups may be substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and part of the carbon atoms of these groups may be substituted with oxygen atoms and sulfur atoms. , Nitrogen atom and other heteroatom groups, as a result, it can also contain hydroxyl, cyano, carbonyl, ether bond, ester bond, sulfonate bond, carbonate bond, lactone ring, sultone ring, carboxylic anhydride, halogen Alkyl and so on. Hydrocarbon groups containing heteroatoms include: 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tertiary Alkoxyphenyl such as butoxyphenyl and 3-tertiary butoxyphenyl; Alkoxy groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl and n-butoxynaphthyl Naphthyl; dialkoxynaphthyl such as dimethoxynaphthyl and diethoxynaphthyl; 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-side Oxyethyl, 2-(2-naphthyl)-2-oxyethyl and other aryl-side oxyalkyl groups such as 2-aryl-2-oxyethyl and the like.

R ¹⁰² is a hydrocarbon group having 1 to 40 carbon atoms which may contain a hetero atom. The hydrocarbon group represented by R ¹⁰² may be the same as those exemplified as the hydrocarbon group represented by ^{R 101.} In addition, other specific examples may also include: trifluoromethyl, trifluoroethyl, 2,2,2-trifluoro-1-methyl-1-hydroxyethyl, 2,2,2-trifluoro-1- (Trifluoromethyl)-1-hydroxyethyl and other fluorinated alkyl groups; pentafluorophenyl or 4-trifluoromethylphenyl and other fluorinated aryl groups.

The sulfonate represented by the formula (Z1) can be exemplified as follows, but it is not limited thereto. [化71]

[化72]

The carboxylate represented by the formula (Z2) can be exemplified as follows, but it is not limited thereto. [化73]

When the resist composition of the present invention contains the aforementioned quencher, its content is preferably 0.001-12 parts by mass, more preferably 0.01-8 parts by mass relative to 100 parts by mass of the base resin of component (A). Due to the blending of the quencher, the adjustment of the resist sensitivity will become easier, and the diffusion rate of the acid in the resist film can be suppressed, the resolution can be improved, the sensitivity change after exposure can be suppressed, or the substrate and environmental dependence can be reduced , To improve the exposure latitude, pattern outline, etc. In addition, by adding these quenchers, the adhesion of the substrate can also be improved. The aforementioned quenchers can be used singly or in combination of two or more.

[Surfactant] The resist composition of the present invention may also contain surfactant components that are insoluble or poorly soluble in water and soluble in alkali developing solutions and/or insoluble or poorly soluble in water and alkaline developing solutions. Such a surfactant can refer to (S) definition components described in JP 2010-215608 A and JP 2011-16746 A.

惟，上述式中之Rf、R、M、A、B、C、N僅適用於該式中。For surfactants that are insoluble or hardly soluble in water and alkali developing solutions, among the surfactants described in the aforementioned publication, FC-4430 (manufactured by 3M Corporation), SURFLON (registered trademark) S-381 ( Oxygen represented by AGC SEIMI CHEMICAL (stock), SURFYNOL (registered trademark) E1004 (manufactured by AIR PRODUCTS), KH-20, KH-30 (manufactured by Asahi Glass Co., Ltd.), and the following structural formula (surf-1) Etidine ring-opening polymer. These can be used individually by 1 type or in combination of 2 or more types. [化74]

However, the Rf, R, M, A, B, C, and N in the above formula only apply to this formula.

式中，破折線表示原子鍵，分別為衍生自甘油、三羥甲基乙烷、三羥甲基丙烷及新戊四醇之次結構。In the formula (surf-1), R is an aliphatic group with a valence of 2 to 4 and a carbon number of 2 to 5. Specifically, divalent ones include: ethylene, tetramethylene, propylene, 2 , 2-Dimethyl-1,3-propanediyl, pentamethylene, etc., as for the trivalent or tetravalent one, the following ones can be mentioned. [化75]

In the formula, dashed lines represent atomic bonds, which are substructures derived from glycerol, trimethylolethane, trimethylolpropane, and neopentylerythritol, respectively.

Among them, tetramethylene or 2,2-dimethyl-1,3-propanediyl is preferably used. Rf is trifluoromethyl or pentafluoroethyl, preferably trifluoromethyl. M is an integer of 0 to 3, N is an integer of 1 to 4, and the sum of M and N represents the valence of R, which is an integer of 2 to 4. A is 1, B is an integer of 2-25, and C is an integer of 0-10. B is preferably an integer of 4-20, and C is preferably 0 or 1. In addition, the arrangement of each constituent unit of the aforementioned structure is not limited, and may be a block or randomly bonded. For the production of the surfactant of the partially fluorinated oxetane ring-opening polymer system, please refer to the specification of U.S. Patent No. 5650483, etc. for details.

[Pattern Formation Method] The present invention further provides a pattern formation method using the aforementioned resist composition. When the resist composition of the present invention is used to form a pattern, a well-known photolithography technique can be used for implementation. Specifically, for example, the resist composition of the present invention is applied to the substrate (Si, SiO ₂ , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective Film, etc.), or the substrate used for mask circuit manufacturing (Cr, CrO, CrON, MoSi ₂ , SiO ₂ etc.), so that the film thickness becomes 0.05-2μm, and then the heating plate is preferably 60-150℃ , 1-10 minutes, pre-bake at 80-140℃, 1-5 minutes better, to form a resist film.

Then, the mask used to form the target pattern is blocked on the aforementioned resist film, and irradiated with high-energy rays such as KrF excimer laser, ArF excimer laser, EUV and EB with a wavelength of 3-15nm, so that the exposure is suitable 1 to 200 mJ/cm ² , more preferably 10 to 100 mJ/cm ² , or preferably 0.1 to 100 μC/cm ² , more preferably 0.5 to 50 μC/cm ^2. In addition to the usual exposure method, the exposure method can also be carried out by inserting a liquid with a refractive index of 1.0 or higher between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used. Then, perform post-exposure bake (PEB) on the hot plate at 60-150°C for 1 to 5 minutes, and more preferably at 80-140°C for 1 to 3 minutes. Then use the developer of an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH), which is preferably 0.1 to 5 mass%, and more preferably 2 to 3 mass%, or use an organic solvent developer such as butyl acetate, and use dip Commonly used methods such as) method, puddle method, spray method, etc. are preferably developed for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, thereby forming a target pattern on the substrate.

The aforementioned water-insoluble protective film is used in order to prevent elution from the resist film and to improve the water slidability of the film surface, and it is roughly divided into two types. One is an organic solvent peeling type that needs to be peeled off with an organic solvent that does not dissolve the resist film before alkali development, and the other is an alkali that is soluble in an alkali developer and removes the protective film when removing the soluble part of the resist film. Soluble type. The latter is based on a polymer compound with 1,1,1,3,3,3-hexafluoro-2-propanol residues that is insoluble in water and soluble in an alkali developer, and is dissolved in a carbon number of 4 The above-mentioned alcohol-based solvents, ether-based solvents with 8 to 12 carbon atoms, and mixed solvents thereof are particularly preferred. It can also be prepared by dissolving the aforementioned surfactant which is insoluble in water and soluble in alkali developer in alcohol solvents with 4 or more carbons, ether solvents with 8 to 12 carbons, or their mixed solvents. .

In addition, as for the pattern forming method, it is possible to perform postsoak after the photoresist film is formed to extract the acid generator from the surface of the film, or to wash the particles. It can be used to remove the water remaining on the film after exposure (postsoak).

In addition, the developer of the pattern forming method of the present invention can be an alkali aqueous solution such as TMAH, preferably 0.1 to 5% by mass, and more preferably 2 to 3% by mass, as described above, but organic solvents can also be used. At this time, negative tone development of developing/dissolving the unexposed part can be implemented.

In the development of the organic solvent, a group selected from 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, and diisobutyl ketone can be used. Base ketone, methyl cyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, phenyl acetate, Propyl formate, butyl formate, isobutyl formate, pentyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate , Propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate , Benzyl acetate, methyl phenylacetate, benzyl formate, phenethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. As a developer. [Example]

Hereinafter, the present invention will be specifically explained by exemplified examples and comparative examples, but the present invention is not limited to the following examples.

將100g之銨鹽1、68.7g之陽離子中間體1、100g之純水及400g之二氯甲烷混合後，攪拌熟成1小時。分離提取有機層後，以5.7g之陽離子中間體1及100g之純水的混合溶液清洗2次，再以100g之純水清洗5次，再以100g之20wt%甲醇水溶液清洗2次。將得到的有機層濃縮，添加PGMEA後再度濃縮，製成20wt%PGMEA溶液。將得到的PGMEA溶液於室溫攪拌過夜使固體析出後，再添加500g之己烷並攪拌2小時。分濾得到的固體，以200g之己烷淋洗，最後於50℃進行減壓加熱乾燥，獲得104.8g之目的之PAG1(產率88%)。得到的PAG1之¹ HNMR表示於圖1，¹⁹ FNMR表示於圖2。 IR(D-ATR)：ν=3087, 3002, 2906, 2852, 1785, 1727, 1477, 1448, 1344, 1240, 1180, 1103, 1076, 1035, 1010, 997, 943, 750, 684, 642, 551, 522, 501 cm^-1 [1] Synthesis of photo acid generator (PAG) [Example 1-1] [Chemical 76]

After mixing 100 g of ammonium salt 1, 68.7 g of cationic intermediate 1, 100 g of pure water and 400 g of dichloromethane, the mixture was stirred and matured for 1 hour. After the organic layer was separated and extracted, it was washed twice with a mixed solution of 5.7 g of cationic intermediate 1 and 100 g of pure water, then washed with 100 g of pure water 5 times, and then washed with 100 g of 20 wt% methanol aqueous solution twice. The obtained organic layer was concentrated, PGMEA was added and then concentrated again to prepare a 20 wt% PGMEA solution. After the obtained PGMEA solution was stirred at room temperature overnight to precipitate a solid, 500 g of hexane was added and stirred for 2 hours. The obtained solid was separated by filtration, rinsed with 200 g of hexane, and finally heated and dried under reduced pressure at 50° C. to obtain 104.8 g of PAG1 (yield 88%). ^{The 1} HNMR of the obtained PAG1 is shown in FIG. 1, and the ¹⁹ FNMR is shown in FIG. 2. IR(D-ATR): ν=3087, 3002, 2906, 2852, 1785, 1727, 1477, 1448, 1344, 1240, 1180, 1103, 1076, 1035, 1010, 997, 943, 750, 684, 642, 551 , 522, 501 cm ^-1

將417g之銨鹽2、268g之陽離子中間體2、1400g之純水及2000g之二氯甲烷混合後，攪拌熟成1小時。分離提取有機層後，將有機層以600g之純水清洗6次，再以600g之20wt%甲醇水溶液清洗6次。於得到的有機層添加25g之活性碳，並於室溫攪拌過夜。利用過濾將活性碳去除後，將有機層以600g之1%鹽酸清洗1次，再以600g之純水清洗2次，再以600g之1%鹽酸清洗1次，再以600g之純水清洗3次。進一步以600g之0.04eq.的氨水清洗1次，再以600g之純水清洗3次，再以600g之0.5%鹽酸清洗1次，再以600g之純水清洗3次。將有機層濃縮，添加PGMEA後再度濃縮，製成50wt%PGMEA溶液。將濃縮液滴加於3.5L之二異丙醚中使結晶析出。攪拌1小時後，將其分濾，並以二異丙醚淋洗，最後於50℃進行減壓加熱乾燥，獲得535g之目的之PAG2(產率86%)。得到的PAG2之¹ HNMR表示於圖3，¹⁹ FNMR表示於圖4。 IR(D-ATR)：ν=3089, 2907, 2853, 1785, 1729, 1476, 1449, 1344, 1237, 1180, 1104, 1076, 1035, 1010, 947, 761, 707, 681, 642, 585, 551, 525 cm^-1 [Example 1-2] [化77]

After mixing 417 g of ammonium salt 2, 268 g of cationic intermediate 2, 1400 g of pure water, and 2000 g of dichloromethane, the mixture was stirred and matured for 1 hour. After separating and extracting the organic layer, the organic layer was washed with 600 g of pure water 6 times, and then with 600 g of 20 wt% methanol aqueous solution 6 times. 25 g of activated carbon was added to the obtained organic layer, and the mixture was stirred at room temperature overnight. After the activated carbon is removed by filtration, the organic layer is washed once with 600g of 1% hydrochloric acid, then with 600g of pure water twice, then with 600g of 1% hydrochloric acid once, and then with 600g of pure water 3 Second-rate. It was further washed with 600g of 0.04eq. ammonia water once, then with 600g of pure water for 3 times, then with 600g of 0.5% hydrochloric acid for 1 time, and then with 600g of pure water for 3 times. The organic layer was concentrated, PGMEA was added and then concentrated again to prepare a 50wt% PGMEA solution. The concentrated solution was added dropwise to 3.5 L of diisopropyl ether to precipitate crystals. After stirring for 1 hour, it was filtered separately, rinsed with diisopropyl ether, and finally heated and dried under reduced pressure at 50° C. to obtain 535 g of PAG2 (yield 86%). ^{The 1} HNMR of the obtained PAG2 is shown in FIG. 3, and the ¹⁹ FNMR is shown in FIG. 4. IR(D-ATR): ν=3089, 2907, 2853, 1785, 1729, 1476, 1449, 1344, 1237, 1180, 1104, 1076, 1035, 1010, 947, 761, 707, 681, 642, 585, 551 , 525 cm ^-1

[Examples 1-3～1-9] Synthesis of other PAGs (PAG-3～PAG-9) The corresponding raw materials are used to synthesize PAG-3 to PAG-9 by a well-known organic synthesis method.

[化78]

[2] Synthesis of polymers The polymer used in the resist composition of the present invention was synthesized by the method shown below. In addition, the Mw of the obtained polymer is a polystyrene conversion value measured by GPC using THF or DMF as a solvent.

於氮氣環境下，使對羥基苯乙烯(27.8g)、甲基丙烯酸-1-甲基環戊酯(72.2g)、及2,2’-偶氮雙異丁酸二甲酯(6.08g)溶解於PGMEA(155g)，製得溶液。將該溶液於氮氣環境下，歷時6小時滴加於以80℃攪拌之PGMEA(78g)。滴加結束後維持80℃的狀態攪拌2小時，冷卻至室溫後，將反應溶液滴加於正己烷(3000g)。分濾析出的固體，於50℃真空乾燥20小時，以白色粉末固體狀之形式獲得阻劑聚合物1。產量為85g，產率為85%。[Synthesis Example 1] Synthesis of Resistor Polymer 1 [Chemical 79]

In a nitrogen environment, make p-hydroxystyrene (27.8g), 1-methylcyclopentyl methacrylate (72.2g), and dimethyl 2,2'-azobisisobutyrate (6.08g) Dissolved in PGMEA (155g) to prepare a solution. This solution was added dropwise to PGMEA (78 g) stirred at 80°C over 6 hours under a nitrogen atmosphere. After completion of the dropwise addition, stirring was maintained at 80°C for 2 hours, and after cooling to room temperature, the reaction solution was added dropwise to n-hexane (3000 g). The precipitated solid was separated by filtration, and vacuum dried at 50° C. for 20 hours to obtain the resist polymer 1 in the form of a white powder solid. The yield is 85g, and the yield is 85%.

[Synthesis Examples 2 to 7] Synthesis of Resist Polymers 2 to 7 except that the type and blending ratio of monomers were changed, the same method as in Synthesis Example 1 was used to produce the following Resist Polymers 2 to 2 7. [化80]

[3] Preparation of resist composition [Examples 2-1 to 2-40, Comparative Examples 1-1 to 1-38] The onium salts (PAG-1～PAG-9) of the present invention, the photoacid generators PAG-A～PAG-H for comparison, the inhibitor polymers 1～7, and other photoacid generators PAG-X～PAG-Z , Quenching agents Q-1 to Q-4, and alkali-soluble surfactant SF-1, with the composition shown in Tables 1 and 2 below, dissolved in 0.01% by mass containing surfactant A (manufactured by OMNOVA) In the solvent, a solution was prepared, and the solution was filtered with a 0.2 μm Teflon (registered trademark) filter to obtain a resist composition.

[Table 1] Composition Base resin (parts by mass) Acid generator 1 (parts by mass) Acid generator 2 (parts by mass) Other acid generator 1 (parts by mass) Other acid generator 2 (parts by mass) Quenching agent (parts by mass) Fluoropolymer (parts by mass) Solvent 1 (parts by mass) Solvent 2 (parts by mass) Example 2-1 R-1 Resist Polymer 1 (80) PAG-1(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-2 R-2 Resist Polymer 1 (80) PAG-2(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-3 R-3 Resist Polymer 1 (80) PAG-3(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-4 R-4 Resist Polymer 1 (80) PAG-4(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-5 R-5 Resist Polymer 1 (80) PAG-5(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-6 R-6 Resist Polymer 1 (80) PAG-6(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-7 R-7 Resist Polymer 1 (80) PAG-7(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-8 R-8 Resist Polymer 1 (80) PAG-8(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-9 R-9 Resist Polymer 1 (80) PAG-9(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Example 2-10 R-10 Resist Polymer 2 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-11 R-11 Resist polymer 3 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-12 R-12 Resist polymer 4 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-13 R-13 Resist polymer 5 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-14 R-14 Resistor polymer 6 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-15 R-15 Resist polymer 7(80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-16 R-16 Resist Polymer 2 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-17 R-17 Resist polymer 3 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-18 R-18 Resist polymer 4 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-19 R-19 Resist polymer 5 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-20 R-20 Resistor polymer 6 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-21 R-21 Resist polymer 7(80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-22 R-22 Resist Polymer 1 (80) PAG-1(4) PAG-2(2) - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-23 R-23 Resist Polymer 1 (80) PAG-1(4) PAG-3(2) - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-24 R-24 Resist Polymer 1 (80) PAG-1(4) PAG-4(2) - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-25 R-25 Resist Polymer 1 (80) PAG-1(3) - PAG-X(3) - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-26 R-26 Resist Polymer 1 (80) PAG-1(3) - PAG-Y(3) - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-27 R-27 Resist Polymer 1 (80) PAG-1(3) - PAG-Z(3) - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-28 R-28 Resist Polymer 1 (80) PAG-1(3) - PAG-X(2) PAG-Y(2) Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-29 R-29 Resist Polymer 1 (80) PAG-1(3) - PAG-Y(2) PAG-Z(2) Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-30 R-30 Resist Polymer 1 (80) PAG-1(5) - - - Q-2(2) - S-1 (1,380) S-2 (220) Example 2-31 R-31 Resist Polymer 1 (80) PAG-1(5) - - - Q-3(2) - S-1 (1,380) S-2 (220) Example 2-32 R-32 Resist Polymer 1 (80) PAG-1(5) - - - Q-4(2) - S-1 (1,380) S-2 (220) Example 2-33 R-33 Resist Polymer 1 (80) PAG-1(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-34 R-34 Resist Polymer 1 (80) PAG-1(10) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-35 R-35 Resist Polymer 1 (80) PAG-1(20) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-36 R-36 Resist Polymer 1 (80) PAG-1(30) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-37 R-37 Resist Polymer 1 (80) PAG-2(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-38 R-38 Resist Polymer 1 (80) PAG-2(10) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-39 R-39 Resist Polymer 1 (80) PAG-2(20) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Example 2-40 R-40 Resist Polymer 1 (80) PAG-2(30) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220)

[Table 2] Composition Base resin (parts by mass) Acid generator 1 (parts by mass) Acid generator 2 (parts by mass) Other acid generator 1 (parts by mass) Other acid generator 2 (parts by mass) Quenching agent (parts by mass) Fluoropolymer (parts by mass) Solvent 1 (parts by mass) Solvent 2 (parts by mass) Comparative example 1-1 R-41 Resist Polymer 1 (80) PAG-A(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-2 R-42 Resist Polymer 1 (80) PAG-B(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-3 R-43 Resist Polymer 1 (80) PAG-C(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-4 R-44 Resist Polymer 1 (80) PAG-D(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-5 R-45 Resist Polymer 1 (80) PAG-E(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-6 R-46 Resist Polymer 1 (80) PAG-F(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-7 R-47 Resist Polymer 1 (80) PAG-G(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-8 R-48 Resist Polymer 1 (80) PAG-H(5) - - - Q-1(2) - S-1 (1,380) S-2 (220) Comparative example 1-9 R-49 Resistor Polymer 2 (80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-10 R-50 Resist Polymer 2 (80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-11 R-51 Resist Polymer 2 (80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-12 R-52 Resist Polymer 2 (80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-13 R-53 Resist Polymer 2 (80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-14 R-54 Resist polymer 3 (80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-15 R-55 Resist polymer 3 (80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-16 R-56 Resist polymer 3 (80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-17 R-57 Resist polymer 3 (80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-18 R-58 Resist polymer 3 (80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-19 R-59 Resist polymer 4 (80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-20 R-60 Resist polymer 4 (80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-21 R-61 Resist polymer 4 (80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-22 R-62 Resist polymer 4 (80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-23 R-63 Resist polymer 4 (80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-24 R-64 Resist polymer 5 (80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-25 R-65 Resist polymer 5 (80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-26 R-66 Resist polymer 5 (80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-27 R-67 Resist polymer 5 (80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-28 R-68 Resist polymer 5 (80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-29 R-69 Resistor polymer 6 (80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-30 R-70 Resistor polymer 6 (80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-31 R-71 Resistor polymer 6 (80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-32 R-72 Resistor polymer 6 (80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-33 R-73 Resistor polymer 6 (80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-34 R-74 Resist polymer 7(80) PAG-A(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-35 R-75 Resist polymer 7(80) PAG-B(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-36 R-76 Resist polymer 7(80) PAG-C(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-37 R-77 Resist polymer 7(80) PAG-D(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220) Comparative example 1-38 R-78 Resist polymer 7(80) PAG-E(5) - - - Q-1(2) SF-1(5) S-1 (1,380) S-2 (220)

In addition, in Tables 1 and 2, solvents, comparative photoacid generators PAG-A～PAG-H, other photoacid generators PAG-X～PAG-Z, quenchers Q-1～Q-4, and alkali The soluble surfactant (fluoropolymer) SF-1 system is as follows.

･PAG-A～PAG-H: [化81]

･PAG-X～PAG-Z: [化82]

･SF-1: [化83]

･Q-1～Q-4: [化84]

･Solvent: S-1: PGMEA (Propylene Glycol Monomethyl Ether Acetate) S-2: GBL (γ-butyrolactone)

a：(b+b’)：(c+c’)=1：4～7：0.01～1(莫耳比) Mw=1,500･Surface active agent A: 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane･tetrahydrofuran･2,2-dimethyl-1,3-propane Alcohol copolymer (manufactured by OMNOVA) [Chem. 85]

a: (b+b'): (c+c')=1: 4～7: 0.01～1 (mole ratio) Mw=1,500

[4] Evaluation of resist composition: EUV exposure patterning evaluation (hole pattern evaluation) [Examples 3-1 to 3-40, Comparative Examples 2-1 to 2-38] The resist composition (R-1～R-40) of the present invention and the comparative resist composition (R-41～R-78) were applied to BRUWER using CLEAN TRACK Lithius ProZ created by Tokyo Velico SCIENCE company made a 20nm film thickness of the organic anti-reflective film AL-412 on the substrate, and baked it on a hot plate at 105°C for 60 seconds to form a 50nm resist film. Use the EUV exposure machine NXE3300 manufactured by ASML to expose a grid pattern of 27.5nm with a pitch of 46nm on the mask. After exposure, apply a PEB temperature suitable for each resist composition, and spin the wafer while spraying 2. A 38% aqueous solution of tetramethylammonium, developed for a total of 30 seconds, washed away the alkali solution with a water stream, and then the wafer was rotated at a high speed to remove the water.

[Sensitivity evaluation] Observe the prepared resist pattern with CD-SEM CG-5000 manufactured by Hitachi Advanced Technology, and use the exposure amount at which the hole diameter becomes 23nm at a pitch of 46nm as the optimal exposure amount Eop (mJ/cm ² ).

[MEF Evaluation] When the size on the mask is a pitch of 46nm and the grid pattern is 27.5nm, and when observing with CD-SEM, when observing the hole diameter near 23nm, the size on the mask is measured as the pitch of 46nm and the grid pattern is 26.0nm, The CD of the hole pattern at 26.5nm, 27.0nm, 27.5nm, 28.0nm, 28.5nm, 29.0nm. The size on the mask and the slope of the observed CD are regarded as MEF (Mask Error Enhancement Factor). About 3.0 or less is defined as good MEF.

[Evaluation of Dimension Uniformity (CDU)] Observe the hole pattern with CD-SEM CG-5000 manufactured by Hitachi Advanced Technology. With 1 hole per sample, the hole diameter is measured at 32 points, and the length of 49 holes is measured from 1 SEM image. The 3 times value (3σ) of the standard deviation (σ) calculated from the result is obtained, 30 SEM images are obtained, and the average value of the standard deviation is taken as the CDU. The smaller the value of CDU, the better the dimensional uniformity. About 3.2 or less is defined as good CDU.

[table 3] Blocker PEB (℃) Eop (mJ/cm ² ) MEF CDU (nm) Example 3-1 R-1 90 30 2.9 2.8 Example 3-2 R-2 90 33 2.7 2.8 Example 3-3 R-3 95 28 2.9 2.9 Example 3-4 R-4 90 31 2.5 2.6 Example 3-5 R-5 85 35 2.8 2.4 Example 3-6 R-6 90 32 2.5 2.8 Example 3-7 R-7 90 31 2.6 2.6 Example 3-8 R-8 100 28 2.9 2.8 Example 3-9 R-9 90 31 3.0 2.6 Example 3-10 R-10 90 31 2.7 2.7 Example 3-11 R-11 80 34 2.6 2.8 Example 3-12 R-12 90 32 2.9 3.1 Example 3-13 R-13 95 33 2.7 3.0 Example 3-14 R-14 90 31 2.6 2.8 Example 3-15 R-15 100 30 2.7 2.9 Example 3-16 R-16 90 29 2.6 3.1 Example 3-17 R-17 90 33 2.8 3.2 Example 3-18 R-18 85 34 2.9 3.2 Example 3-19 R-19 90 31 3.0 2.7 Example 3-20 R-20 90 30 2.7 2.9 Example 3-21 R-21 85 33 2.6 3.1 Example 3-22 R-22 90 36 2.5 2.9 Example 3-23 R-23 100 30 2.6 2.5 Example 3-24 R-24 90 30 3.0 2.6 Example 3-25 R-25 90 31 2.9 2.7 Example 3-26 R-26 95 34 2.8 2.9 Example 3-27 R-27 90 33 2.7 3.0 Example 3-28 R-28 85 32 3.0 2.7 Example 3-29 R-29 90 31 2.7 2.8 Example 3-30 R-30 90 28 2.6 2.9 Example 3-31 R-31 95 29 2.5 3.0 Example 3-32 R-32 90 35 2.8 2.9 Example 3-33 R-33 105 27 2.9 2.6 Example 3-34 R-34 90 30 2.7 2.6 Example 3-35 R-35 90 31 3.0 2.3 Example 3-36 R-36 80 33 2.8 2.4 Example 3-37 R-37 90 32 2.8 2.7 Example 3-38 R-38 85 36 2.7 2.3 Example 3-39 R-39 90 31 2.9 2.3 Example 3-40 R-40 90 29 2.8 2.4

[Table 4] Blocker PEB (℃) Eop (mJ/cm ² ) MEF CDU (nm) Comparative example 2-1 R-41 90 30 3.5 3.5 Comparative example 2-2 R-42 90 31 3.6 3.6 Comparative example 2-3 R-43 95 33 3.8 3.7 Comparative example 2-4 R-44 90 33 3.9 3.8 Comparative example 2-5 R-45 85 32 4.0 4.0 Comparative example 2-6 R-46 90 29 3.5 3.8 Comparative example 2-7 R-47 90 31 3.6 3.6 Comparative example 2-8 R-48 100 27 3.7 3.6 Comparative example 2-9 R-49 90 30 3.8 3.7 Comparative example 2-10 R-50 90 31 3.6 3.8 Comparative example 2-11 R-51 95 30 3.7 4.0 Comparative example 2-12 R-52 90 33 3.5 4.2 Comparative example 2-13 R-53 85 36 3.6 3.9 Comparative example 2-14 R-54 90 30 4.1 3.7 Comparative example 2-15 R-55 90 31 3.5 3.8 Comparative example 2-16 R-56 80 35 3.6 3.6 Comparative example 2-17 R-57 100 28 3.7 3.8 Comparative example 2-18 R-58 95 27 3.9 3.9 Comparative example 2-19 R-59 90 30 3.8 4.1 Comparative example 2-20 R-60 90 31 3.8 4.0 Comparative example 2-21 R-61 80 33 3.9 3.7 Comparative example 2-22 R-62 85 32 3.6 3.8 Comparative example 2-23 R-63 90 31 3.7 3.7 Comparative example 2-24 R-64 90 30 3.8 3.9 Comparative example 2-25 R-65 90 31 3.9 3.9 Comparative example 2-26 R-66 95 28 3.8 4.0 Comparative example 2-27 R-67 90 29 3.8 3.8 Comparative Example 2-28 R-68 95 30 3.7 3.7 Comparative example 2-29 R-69 90 33 3.9 3.6 Comparative example 2-30 R-70 90 33 4.1 3.6 Comparative example 2-31 R-71 90 32 3.5 3.8 Comparative example 2-32 R-72 85 35 3.6 3.8 Comparative example 2-33 R-73 90 30 3.9 3.9 Comparative example 2-34 R-74 100 29 4.0 4.1 Comparative example 2-35 R-75 90 30 3.7 3.8 Comparative example 2-36 R-76 90 31 3.8 3.7 Comparative example 2-37 R-77 105 33 4.0 3.7 Comparative example 2-38 R-78 90 31 3.8 3.9

From the results shown in Table 3, it can be seen that the resist composition (Example) of the present invention has good sensitivity and excellent MEF and CDU. On the other hand, as shown in Table 4, conventional photoacid generators PAG-A to PAG-E (refer to Patent Documents 1 to 4), PAG-F, PAG-H, W2 The resist composition of PAG-G and PAG-H containing heteroatoms (comparative example) has insufficient MEF and CDU. In summary, it is shown that the resist composition of the present invention is particularly suitable as a material for EUV lithography.

In addition, the present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiments are just examples, and those having substantially the same constitution as the technical idea described in the scope of the patent application of the present invention and exerting the same functions and effects are all intended to be included in the technical scope of the present invention.

none

[Fig. 1] A diagram showing ^{the 1 HNMR spectrum of PAG1 obtained in Example 1-1.} [Fig. 2] A diagram showing ^{the 19 FNMR spectrum of PAG1 obtained in Example 1-1.} [Figure 3] A diagram showing ^{the 1} HNMR spectrum of PAG2 obtained in Example 1-2. [Figure 4] A diagram showing ^{the 19} FNMR spectrum of PAG2 obtained in Example 1-2.

Claims (11)

A resist composition characterized by containing: (A) a resin containing a repeating unit with an acid-labile group, and further containing at least one repeating unit with an aromatic substituent, (B) general formula (B-1) ) Represents the photoacid generator, and (C) solvent;

In the formula, W ₁ represents a heteroatom-containing cyclic divalent hydrocarbon group with 4 to 12 carbons; W ₂ represents a carbon 4 to 14 cyclic monovalent hydrocarbon group without heteroatoms; Rf is selected from the following formula ( Rf-1), and the group represented by (Rf-3)~(Rf-6); M ⁺ represents onium cation;

* Represents the atomic bond with the carbonyloxy group. _{The resist composition of claim 1, wherein W 1} in the general formula (B-1) is a cyclic divalent hydrocarbon group containing a lactone ring structure with 6 to 12 carbon atoms. Such as the resist composition of claim 1 or 2, wherein W ₂ in the general formula (B-1) is a multicyclic monovalent hydrocarbon group with 7 to 14 carbon atoms and no heteroatoms. The resist composition of claim 1 or 2, wherein, in the resin of the component (A), one of the repeating units having an aromatic substituent is a repeating unit represented by the following formula (A-1);

In the formula, R ^A represents a hydrogen atom or a methyl group; R ₆₁ represents a hydrogen atom, or a linear, branched, or cyclic hydrocarbon group with 1 to 10 carbon atoms that can also be inserted into a heteroatom _{; R 62 represents that a hetero atom can also be inserted.} A linear or branched or cyclic hydrocarbon group with 1~8 carbon atoms; t is an integer of 1~3, u is an integer conforming to u≦5+2s-t; s is 0 or 1; L ₁ means Single bond, or any one of -C(=O)O-, -C(=O)NH-. The resist composition of claim 1 or 2, wherein, in the resin of the component (A), one of the repeating units having an aromatic substituent is the following general formula (A-2) to (A- 4) The repeating unit represented;

In the formula, R ^{A is} independently a hydrogen atom or a methyl group, R ²⁰¹ is a single bond, a phenylene group, -OR ²¹⁰ -, or -C(=O)-Z ² -R ²¹⁰ -; Z ² is an oxygen atom Or NH, R ²¹⁰ is a linear or branched or cyclic alkylene group, alkenylene group or phenylene group with carbon number 1~6, and may also contain carbonyl group (-CO-), ester group (-COO) -), ether group (-O-) or hydroxyl group; L ₂ represents a single bond, or -Z ³ -C(=O)-O-, Z ³ represents a straight line with 1 to 20 carbon atoms that can also be substituted by a heteroatom Chain or branched or cyclic divalent hydrocarbon group; Z ¹ is a single bond, methylene, ethylidene, phenylene, fluorinated phenylene, -OR ²¹¹ -, or -C(=O ) -Z ⁴ -R ²¹¹ -; Z ⁴ is an oxygen atom or NH, R ²¹¹ is a linear or branched or cyclic alkylene, alkenylene or phenylene group with 1 to 6 carbon atoms, and also May contain carbonyl, ester, ether or hydroxyl; M ^- represents a non-nucleophilic relative ion; R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , and R ²⁰⁹ each independently represent also A monovalent hydrocarbon group that can be substituted by heteroatoms or can be inserted into a straight-chain carbon number of 1 to 20, or a branched or cyclic carbon number of 3 to 20; also, R ²⁰² and R ²⁰³ can also be bonded to each other The combination and the sulfur atom in the formula together form a ring, or ^{any two or more of R 204} , R ²⁰⁵ and R ²⁰⁶ , or any two or more of R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ can also be mutually bonded and combined The sulfur atoms in the formula together form a ring; however, the repeating units represented by the general formulas (A-2) to (A-4) have more than one aromatic substituent. For example, the resist composition of claim 1 or 2 further contains component (D), which is a resin different from the resin of component (A), and is selected from the following formulas (D-1) and (D-2) And (D-3) a fluorine-containing resin of at least one of the repeating units;

In the formula, R ^{A is} each independently a hydrogen atom or a methyl group; R ₅₁ and R ₅₂ are each independently a hydrogen atom, or a linear, branched, or cyclic monovalent hydrocarbon group with 1 to 10 carbon atoms; R ₅₃ It is a single bond, or a linear or branched divalent hydrocarbon group with carbon number of 1 to 5; R ₅₄ , R ₅₅ and R ₅₆ are each independently a hydrogen atom, or linear or branched or cyclic carbon number 1-15 monovalent hydrocarbon group, fluorinated monovalent hydrocarbon group or acyl group, or acid labile group; when R ₅₄ , R ₅₅ and R ₅₆ are monovalent hydrocarbon group or fluorinated monovalent hydrocarbon group, some of their carbon atoms may be Substitution by ether or carbonyl; R ₅₇ is a linear or branched or cyclic (v+1) hydrocarbon group or fluorinated hydrocarbon group with 1 to 20 carbon atoms; v is an integer of 1 to 3. A pattern forming method, characterized by comprising the following steps: coating the resist composition of any one of claims 1 to 6 on a substrate and performing heat treatment to form a resist film, and the resist film with high energy Radiation is used for exposure, and the exposed resist film is developed using a developer. According to the pattern forming method of claim 7, wherein the high-energy ray is an ArF excimer laser with a wavelength of 193 nm or a KrF excimer laser with a wavelength of 248 nm. The pattern forming method of claim 7 or 8, wherein the exposure is an immersion exposure performed by inserting a liquid with a refractive index of 1.0 or more between the resist film and the projection lens. Such as the pattern forming method of claim 9, which further forms a protective film on the resist film, and inserts the liquid between the protective film and the projection lens to perform immersion exposure. Such as the pattern forming method of claim 7, wherein the high-energy rays are electron beams or extreme ultraviolet rays with a wavelength of 3-15 nm.

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