Chemical amplification resist composition, blank photomask, method for forming resist pattern, and method for producing polymer compound

Abstract

The present invention relates to a chemical amplification resist composition, a blank photomask, a resist pattern forming method, and a method for producing a polymer compound. The present invention aims to provide a chemical amplification resist composition that can satisfy good resolution, pattern shape, line edge roughness, and can suppress development residue defects that can become a cause of mask defects, and a resist pattern forming method using the same. The means for solving the problem is a chemical amplification resist composition characterized by containing: (A) a polymer compound containing one or two or more kinds of repeating units, and at least one or more kinds of repeating units among the repeating units being a repeating unit polymerized from 2 to 6 polymers of a residual oligomer of 1000 ppm or less of a polymerizable monomer.

Description

TECHNICAL FIELD

[0001] The present application relates to a chemically amplified resist composition and a resist pattern forming method using the same. BACKGROUND

[0002] In recent years, with the high integration and high speed of LSI, the miniaturization of pattern rules is also rapidly progressing. In the processing of patterns of 0.2 μm or less, a chemically amplified resist using acid as a catalyst is mainly used. Also, high-energy rays such as ultraviolet rays, extreme ultraviolet rays, and electron beams (EB) are used as exposure sources, and in particular, EB lithography, which is a super-fine processing technique, is indispensable in the processing method for producing a blank photomask for a photomask for semiconductor manufacturing.

[0003] A large number of polymers having an aromatic skeleton with an acidic side chain, such as polyhydroxystyrene, are useful as resist materials for KrF excimer lasers, but they exhibit a large absorption for light having a wavelength of about 200 nm, and thus cannot be used as resist materials for ArF excimer lasers. However, in the case of resist materials for EB or extreme ultraviolet (EUV) which are powerful techniques for forming patterns smaller than the processing limit of ArF excimer lasers, they are important materials from the viewpoint of obtaining high etching resistance.

[0004] In the case of a resist composition used in such optical lithography, there are a positive type in which an exposed portion is dissolved to form a pattern, and a negative type in which a residual exposed portion is left to form a pattern, and they can be easily used in response to the shape of a necessary resist pattern. A chemically amplified negative resist composition generally has a high molecular compound which is dissolved in an aqueous alkaline developer, an acid generator which is decomposed by exposure light and generates acid, and a crosslinking agent which forms crosslinks between the high molecular compound with acid as a catalyst and makes the high molecular compound insoluble in the aforementioned developer (optionally, the high molecular compound and the crosslinking agent are integrated), or a compound which becomes insoluble in the aforementioned developer due to a change in polarity of the high molecular compound, and in addition, an alkaline compound for controlling the diffusion of acid generated by exposure is generally added.

[0005] As the alkali-soluble unit of the high-molecular compound constituting the aforementioned alkali developer which is soluble in water, a unit derived from a phenol can be exemplified. In the past, many types of positive resist compositions, negative resist compositions, especially for exposure to KrF excimer laser light, have been developed. However, they have not been used for ArF excimer laser light because the unit derived from a phenol does not have light transmissivity when the exposure light is in a wavelength of 150 to 220 nm. However, in recent years, positive and negative resist compositions for short wavelength exposure such as EB, EUV, and the like, which are exposure methods for obtaining finer patterns, have again attracted attention, and have been reported in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

[0006] In addition, in the aforementioned photolithography, various improvements such as the selection, combination, and processing conditions of the acid generator, acid diffusion control agent, i.e., basic compound, used in the resist composition, and the like, for the purpose of resist sensitivity, control of pattern profile, have been gradually investigated. For example, they have been reported in Patent Document 5 and Patent Document 6.

[0007] On the other hand, with the progress of the miniaturization of the pattern, defects caused by the resist residue after development have become a problem, and since they are a major cause of scum residue and bridging between resist patterns, there are concerns that the yield, which is important for semiconductor manufacturing processes, will decrease, and improvements in defect reduction are strongly desired. In terms of the improvement of the formulation, removal of unreacted monomers in the polymer has been exemplified in Patent Document 7 and Patent Document 8, or removal methods using filtration have been exemplified in Patent Document 9 and Patent Document 10. In terms of the method for removing unreacted monomers in the polymer, a special crystallization step, water washing and liquid separation, and the like are used, but there are concerns that the essential components are also removed, changing the inherent properties of the polymer, or there are problems such as a decrease in yield and the difficulty of removing low-molecular components from the polymer as desired.

[0008] In addition, column chromatography and filtration have problems in productivity, and it is difficult to completely remove oligomers of the degree of dimer to octamer. In fact, the removal of oligomer components, which have an influence on the development residue, is more important than monomer components, and in advanced lithography in semiconductor processes after the 14 nm node, these methods are still insufficient, and further improvements are required.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] [Patent Document 1] Japanese Patent Application Laid-Open (JP A) No. 2006-201532

[0012] [Patent Document 2] Japanese Patent Application Laid-Open (JP A) No. 2006-215180

[0013] [Patent Document 1] Japanese Patent Application Laid-Open (JP A) No. 2007- 273 1 17

[0014] [Patent Document 2] Japanese Patent Application Laid-Open (JP A) No. 2007- 273 1 18

[0015] [Patent Document 3] Japanese Patent Application Laid-Open (JP A) No. 2008- 249762

[0016] [Patent Document 4] Japanese Patent Application Laid-Open (JP A) No. 2008- 95009

[0017] [Patent Document 5] Japanese Patent Application Laid-Open (JP A) No. 2016- 65016

[0018] [Patent Document 6] Japanese Patent Application Laid-Open (JP A) No. 2016- 200805

[0019] [Patent Document 7] Japanese Patent Application Laid-Open (JP A) No. 2003- 270788

[0020] [Patent Document 8] Japanese Patent Application Laid-Open (JP A) No. 2006- 274276 SUMMARY

[0021] PROBLEMS TO BE SOLVED BY THE INVENTION

[0022] The present application has been achieved in view of the foregoing, and aims to provide a chemically amplified resist composition which can satisfy good resolution, pattern shape, line edge roughness, and can suppress development residue defects which become a cause of mask defects, and a resist pattern forming method using the same.

[0023] MEANS FOR SOLVING THE PROBLEMS

[0024] To solve the above problems, the present application provides a chemically amplified resist composition, comprising:

[0025] (A) a high molecular compound containing one or two or more kinds of repeating units, and at least one or more kinds of repeating units among the foregoing repeating units are repeating units polymerized from a polymerizable monomer having an oligomer content of 1000 ppm or less.

[0026] If so, since purification is not performed at the stage of the polymer, but the polymer is a material in which the oligomer component has been suppressed at the stage of the monomer before polymerization, it is a chemically amplified resist composition which can satisfy good resolution, pattern shape, line edge roughness, and can suppress development residue defects which become a cause of mask defects.

[0027] Also, the aforementioned chemically amplified resist composition is a chemically amplified positive resist composition, and the aforementioned (A) component is preferably a high molecular compound containing a repeating unit A1 represented by the following general formula (Al), and the aforementioned repeating unit A1 is preferably a repeating unit obtained by polymerizing a polymerizable monomer having a residual oligomer of 2 to 6 polymers of 1000 ppm or less.

[0028] [Chemical Formula 1]

[0029]

[0030] wherein R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R 12 are each independently a halogen atom, a linear or branched or cyclic acyloxy group having 2 to 8 carbon atoms which can be substituted by a halogen, a linear or branched or cyclic alkyl group having 1 to 6 carbon atoms which can be substituted by a halogen, or a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms which can be substituted by a halogen. A 2 is a single bond, or a linear or branched or cyclic alkylene group having 1 to 11 carbon atoms, and an ether bond or an ester bond can be inserted between carbon-carbon bonds. s is 0 or 1. t is an integer of 0 to 2. c is an integer satisfying 0 < c < 5 + 2t - e. d is 0 or 1. e is an integer of 1 to 3. r is 0 or 1. X is an acid labile group when e is 1, and is a hydrogen atom or an acid labile group when e is 2 or more, but at least one of them is an acid labile group.

[0031] Also, the aforementioned chemically amplified resist composition is a chemically amplified negative resist composition, and the aforementioned (A) component is preferably a high molecular compound containing a repeating unit A2 represented by the following general formula (A2), and the aforementioned repeating unit A2 is preferably a repeating unit obtained by polymerizing a polymerizable monomer having a residual oligomer of 2 to 6 polymers of 1000 ppm or less.

[0032] [Chemical Formula 2]

[0033]

[0034] wherein R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. A 1 is a single bond, or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and -CH2- constituting the saturated hydrocarbylene group can be substituted by -O-. R 1 are each independently a halogen atom, a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms which can be substituted by a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which can be substituted by a halogen atom, or a saturated hydrocarbyloxy group having 1 to 6 carbon atoms which can be substituted by a halogen atom. W 1R1and R2are each independently a hydrogen atom, a carbon number 1 to 10 aliphatic hydrocarbon group, or an aryl group which can also have a substituent, and -CH2- constituting the aliphatic hydrocarbon group can also be replaced with -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-. Rxand Ryare each independently a hydrogen atom, a carbon number 1 to 15 saturated hydrocarbon group which can also be substituted with a hydroxyl group or a saturated hydrocarbon group oxy group, or an aryl group which can also have a substituent. However, Rxand Ryare not simultaneously a hydrogen atom. Also, Rxand Ryare bonded to each other and form a ring together with the carbon atom to which they are bonded. y is an integer of 0 to 2. u is 0 or 1. f is an integer satisfying 0

[0035] These repeating units which initiate a reaction using the action of an acid generated by exposure have a large influence on defects in the resist composition. Therefore, by inhibiting oligomers in the polymerizable monomer which provides these repeating units, the effects of the present application can be maximized.

[0036] Also, the aforementioned (A) component can also be a high molecular compound containing a repeating unit A3 represented by the following general formula (A3).

[0037] [Chemical Formula 3]

[0038]

[0039] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 11 are each independently a halogen atom, a carbon number 2 to 8 saturated hydrocarbon group carbonyloxy group which can also be substituted with a halogen atom, a carbon number 1 to 6 saturated hydrocarbon group which can also be substituted with a halogen atom, or a carbon number 1 to 6 saturated hydrocarbon group oxy group which can also be substituted with a halogen atom. A 1 is a single bond or a carbon number 1 to 10 saturated hydrocarbylene group, and -CH2- constituting the saturated hydrocarbylene group can also be replaced with -O-. s is 0 or 1. w is an integer of 0 to 2. a is an integer satisfying 0

[0040] Also, the aforementioned (A) component can also be a high molecular compound containing at least one kind selected from repeating units A4 to A11 represented by the following general formulas (A4) to (A11).

[0041] [Chemical Formula 4]

[0042]

[0043] In the formula, R B are each independently a hydrogen atom or a methyl group. Z 1 is a single bond, a carbon number 1 to 6 aliphatic hydrocarbylene group, a phenylene group, a naphthylene group, or a carbon number 7 to 18 group obtained by combining them, -O-Z 11-C(=O)-O-Z 11 -C(=O)-NH-Z 11 -Z 11 is an aliphatic hydrocarbylene group having 1 to 6 carbons, or a phenylene group, a naphthylene group, or a group having 7 to 18 carbons obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 2 is a single bond or -Z 21 -C(=O)-O- 21 is a hydrocarbylene group having 1 to 20 carbons which can also contain a hetero atom. Z 3 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -O-Z 31 -C(=O)-O-Z 31 -C(=O)-NH-Z 31 -Z 31 is an aliphatic hydrocarbylene group having 1 to 6 carbons, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having 7 to 20 carbons obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 4 is a single bond or a hydrocarbylene group having 1 to 30 carbons which can also contain a hetero atom. k 1 and k 2 are each independently 0 or 1, but, when Z 4 is a single bond, k 1 and k 2 are 0. R 21 to R 38 are each independently a hydrocarbon group having 1 to 20 carbons which can also contain a hetero atom. Also, R 21 and R 22 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded, and R 23 and R 24 , R 26 and R 27 , or R 29 and R 30 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. R HF is a hydrogen atom or a trifluoromethyl group. Xa - is a non-nucleophilic counter ion.

[0044] Also, the aforementioned (A) component can also be a high molecular compound containing at least one of repeating units A12 to A14 selected from the group consisting of general formulae (A12), (A13), and (A14).

[0045] [Chemical Formula 5]

[0046]

[0047] in the formula, RA It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 13 and R 14 Each of the following is independently a hydroxyl group, a halogen atom, an acetoxy group, a linear or branched or cyclic acyloxy group having 2 to 8 carbon atoms that may also be substituted with a halogen, a linear or branched or cyclic alkyl group having 1 to 8 carbon atoms that may also be substituted with a halogen, a linear or branched or cyclic alkoxy group having 1 to 8 carbon atoms that may also be substituted with a halogen, or a linear or branched or cyclic alkyl carbonyloxy group having 2 to 8 carbon atoms that may also be substituted with a halogen. R 15 It can be an acetyl group, an acetoxy group, a straight-chain, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a straight-chain, branched, or cyclic alkoxy group having 1 to 20 carbon atoms, a straight-chain, branched, or cyclic acyloxy group having 2 to 20 carbon atoms, a straight-chain, branched, or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a sulfinyl group, or a sulfonyl group. A 3 It is a single-bonded, straight-chain, branched, or cyclic alkylene group with 1 to 10 carbon atoms, and may also have ether bonds inserted between carbon-carbon bonds. o and p are independent integers from 0 to 4. h is an integer of 0 or 1. j is an integer from 0 to 5. k is an integer from 0 to 2.

[0048] Such a polymeric compound can be ideally used as component (A) in this invention.

[0049] Furthermore, the aforementioned chemically amplified resist composition is a chemically amplified positive resist composition, and the aforementioned component (A) is preferably a polymeric compound containing repeating unit A1 represented by the aforementioned general formula (A1) and repeating unit A3 represented by the following general formula (A3), but not containing repeating units A4 to A11 represented by the following general formulas (A4) to (A11).

[0050] [Chemistry 6]

[0051]

[0052] In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 11 Each of the following can be independently a halogen atom, a 2-8 carbonyl carbonyl group that can be substituted by a halogen atom, a 1-6 carbonyl group that can be substituted by a halogen atom, or a 1-6 carbonyl carbonyl group that can be substituted by a halogen atom. 1 It is a single bond or a saturated hydrocarbon group with 1 to 10 carbon atoms, and the -CH2- constituting the saturated hydrocarbon group can also be replaced by -O-. s is 0 or 1. w is an integer from 0 to 2. a is an integer satisfying 0 ≤ a ≤ 5 + 2w - b. b is an integer from 1 to 3.

[0053] [Chemistry 7]

[0054]

[0055] in the formula, R B are each independently a hydrogen atom or a methyl group. Z 1 is a single bond, an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, -O-Z 11 -, -C(=O)-O-Z 11 -, or -C(=O)-NH-Z 11 , Z 11 is an aliphatic hydrocarbylene group having a carbon number of 1 to 6, or a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 2 is a single bond or -Z 21 -C(=O)-O-, Z 21 is a hydrocarbylene group having a carbon number of 1 to 20 which can also contain a hetero atom. Z 3 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -O-Z 31 -, -C(=O)-O-Z 31 -, or -C(=O)-NH-Z 31 , Z 31 is an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having a carbon number of 7 to 20 obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 4 is a single bond or a hydrocarbylene group having a carbon number of 1 to 30 which can also contain a hetero atom. k 1 and k 2 are each independently 0 or 1, but, Z 4 when k 1 and k 2 are 0. R 21 to R 38 are each independently a hydrocarbon group having a carbon number of 1 to 20 which can also contain a hetero atom. Also, R 21 and R 22 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded, and R 23 and R 24 , R 26 and R 27 , or R 29 and R 30 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. R HF is a hydrogen atom or a trifluoromethyl group. Xa - is a non-nucleophilic counter ion.

[0056] When the chemically amplified resist composition of the present application is used as a chemically amplified positive resist composition, the component (A) can be such.

[0057] Further, when the chemically amplified resist composition is a chemically amplified negative resist composition, the component (A) is preferably a high molecular compound containing the repeating unit A2 represented by the general formula (A2) and the repeating unit A3 represented by the following general formula (A3) and not containing the repeating units A4 to A11 represented by the following general formulae (A4) to (A11).

[0058] [Chemical Formula 8]

[0059]

[0060] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R 11 are each independently a halogen atom, a carbons number 2 to 8 saturated hydrocarbylcarbonyloxy group which can be substituted by a halogen atom, a carbons number 1 to 6 saturated hydrocarbyl group which can be substituted by a halogen atom, or a carbons number 1 to 6 saturated hydrocarbyloxy group which can be substituted by a halogen atom. A 1 is a single bond or a carbons number 1 to 10 saturated hydrocarbylene group, and -CH2- constituting the saturated hydrocarbylene group can also be substituted by -O-. s is 0 or 1. w is an integer of 0 to 2. a is an integer satisfying 0 < a < 5 + 2w - b. b is an integer of 1 to 3.

[0061] [Chemical Formula 9]

[0062]

[0063] In the formula, R B are each independently a hydrogen atom or a methyl group. Z 1 is a single bond, a carbons number 1 to 6 aliphatic hydrocarbylene group, a phenylene group, a naphthylene group or a carbons number 7 to 18 group obtained by combining them, -O-Z 11 -, -C(=O)-O-Z 11 - or -C(=O)-NH-Z 11 -, Z 11 is a carbons number 1 to 6 aliphatic hydrocarbylene group, or a phenylene group, a naphthylene group or a carbons number 7 to 18 group obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group. Z 2 is a single bond or -Z 21 -C(=O)-O-, Z 21 is a carbons number 1 to 20 hydrocarbylene group which can also contain a hetero atom. Z 3 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted by a trifluoromethyl group, -O-Z 31 -, -C(=O)-O-Z 31- or -C(=O)-NH-Z 31 -, Z 31 is an aliphatic hydrocarbylene group having 1 to 6 carbons, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having 7 to 20 carbons obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 4 is a single bond or an aliphatic hydrocarbylene group having 1 to 30 carbons which can also contain a hetero atom. k 1 and k 2 are each independently 0 or 1, but, when Z 4 is a single bond, k 1 and k 2 are 0. R 21 to R 38 are each independently a hydrocarbon group having 1 to 20 carbons which can also contain a hetero atom. Also, R 21 and R 22 can be bonded to each other and form a ring together with the sulfur atom to which they are bonded, and R 23 and R 24 , R 26 and R 27 , or R 29 and R 30 can be bonded to each other and form a ring together with the sulfur atom to which they are bonded. R HF is a hydrogen atom or a trifluoromethyl group. Xa - is a non-nucleophilic counter ion.

[0064] Also, the aforementioned (A) component is a high molecular compound containing either one of the repeating unit represented by the following general formula (A2-1) and the repeating unit represented by the following general formula (A2-2), or both, and containing the repeating unit represented by the following general formula (A3-1), and the repeating unit represented by the following general formula (A5-1) is desirable.

[0065] [Chemical Formula 10]

[0066]

[0067] in the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Rxand Ryare each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 15 carbons which can also be substituted with a hydroxyl group or a saturated hydrocarbon oxy group, or an aryl group which can also have a substituent. However, Rxand Ryare not simultaneously a hydrogen atom. Also, Rxand Ry B are each independently a hydrogen atom or a methyl group. Z 2 is a single bond or -Z 21 -C(=O)-O-, Z 21 is an aliphatic hydrocarbylene group having 1 to 20 carbons which can also contain a hetero atom. R23 ~R 25 respectively and independently are a hydrocarbon group of 1 to 20 carbon numbers which can also contain hetero atoms. Also, R 23 and R 24 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

[0068] When the chemically amplified resist composition of the present application is used as a chemically amplified negative resist composition, the (A) component can be such that:

[0069] Also, the high molecular compound of the aforementioned (A) component is a polymer of two or more polymerizable monomers, and it is desirable that the total of the residual oligomers of 2 to 6 polymers contained in all of the aforementioned polymerizable monomers be 5000 ppm or less.

[0070] When the (A) component is such, the occurrence of development residue defects can be more reliably suppressed.

[0071] Also, it is desirable that the chemically amplified resist composition of the present application further contain a (B) acid generator.

[0072] When adjusted to be such, it is more suitable as a chemically amplified resist composition.

[0073] Also, the present application provides a blank photomask on which the aforementioned chemically amplified resist composition is coated.

[0074] The chemically amplified resist composition of the present application is particularly useful in the formation of a pattern using a blank photomask as a substrate.

[0075] Also, the present application provides a method for forming a resist pattern, comprising:

[0076] (1) a step of forming a resist film on a substrate using the aforementioned chemically amplified resist composition,

[0077] (2) a step of irradiating a pattern to the aforementioned resist film using a high energy ray, and

[0078] (3) a step of developing the aforementioned resist film on which the pattern has been irradiated using an alkali developer.

[0079] When the pattern forming method is such, since the chemically amplified resist composition of the present application is used, good resolution, pattern shape, line edge roughness can be satisfied, and at the same time, development residue defects which can become a cause of mask defects can be suppressed.

[0080] At this time, it is desirable that the aforementioned high energy ray be set to an ArF excimer laser, a KrF excimer laser, an extreme ultraviolet ray, or an electron beam.

[0081] It is desirable that such be used as the high energy ray.

[0082] Further, it is desirable that the topmost surface of the aforementioned substrate is composed of a material containing at least one of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

[0083] The chemical amplification resist composition of the present application can be used regardless of the type of substrate and reduces development residue.

[0084] Further, the present application provides a method for producing a high molecular compound containing one or two or more repeating units, which is used in a chemical amplification resist composition, by polymerizing a polymerizable monomer having at least one or more residual oligomers of a 2-6 polymer of 1000 ppm or less to obtain the aforementioned high molecular compound.

[0085] If so, by using a material in which the oligomer component is suppressed at the stage of monomer before polymerization, rather than at the stage of polymer, a high molecular compound used in a chemical amplification resist composition that can satisfy good resolution, pattern shape, line edge roughness, and can suppress development residue defects that can become a cause of mask defects can be produced.

[0086] Further, it is desirable that at least one of the repeating units of the polymerizable monomer having at least one or more residual oligomers of a 2-6 polymer of 1000 ppm or less is a repeating unit A1 represented by the following general formula (Al).

[0087] [Chemical Formula 11]

[0088]

[0089] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 12 are each independently a halogen atom, a linear or branched or cyclic acyloxy group having 2 to 8 carbon atoms which can be substituted with a halogen, a linear or branched or cyclic alkyl group having 1 to 6 carbon atoms which can be substituted with a halogen, or a linear or branched or cyclic alkoxy group having 1 to 6 carbon atoms which can be substituted with a halogen. A 2 is a single bond, or a linear or branched or cyclic alkylene group having 1 to 11 carbon atoms, and an ether bond or an ester bond can be inserted between the carbon-carbon bonds. s is 0 or 1. t is an integer of 0 to 2. c is an integer satisfying 0 ≤ c ≤ 5 + 2t - e. d is 0 or 1. e is an integer of 1 to 3. r is 0 or 1. X is an acid-labile group when e is 1, and is a hydrogen atom or an acid-labile group when e is 2 or more, but at least one of them is an acid-labile group.

[0090] Further, it is desirable that the residual oligomer from the aforementioned 2 to 6 polymers be 1000 ppm or less of at least one of the repeating units of the polymerizable monomer represented by the following General Formula (A2).

[0091] [Chemical 12]

[0092]

[0093] wherein R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. A 1 is a single bond, or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and -CH2- constituting the saturated hydrocarbylene group can also be replaced with -O-. R 1 are each independently a halogen atom, a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms which can also be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which can also be substituted with a halogen atom, or a saturated hydrocarbyloxy group having 1 to 6 carbon atoms which can also be substituted with a halogen atom. W 1 is a hydrogen atom, or an aliphatic hydrocarbyl group having 1 to 10 carbon atoms, or an aryl group which can also have a substituent, and -CH2- constituting the aliphatic hydrocarbyl group can also be replaced with -O-, -C(=O)-, -O-C(=O)- or -C(=O)-O-. Rxand Ryare each independently a hydrogen atom, a saturated hydrocarbyl group having 1 to 15 carbon atoms which can also be substituted with a hydroxyl group or a saturated hydrocarbyloxy group, or an aryl group which can also have a substituent. However, Rxand Ryare not simultaneously a hydrogen atom. Further, Rxand Ry

[0094] These repeating units which initiate a reaction using the action of an acid generated by exposure have a large influence on defects in the resist composition, and therefore it is desirable to suppress oligomers of the polymerizable monomer which provide these repeating units.

[0095] [Effects of the Invention]

[0096] The chemically amplified resist composition of the present application, by containing a polymer which is not purified at the stage of the polymer, but is a polymer of a material in which the oligomer component has been suppressed at the stage of the monomer before polymerization, can provide a chemically amplified resist composition and a method for forming a resist pattern which can satisfy good resolution, pattern shape, line edge roughness, and can suppress a development residue defect which can become a cause of a mask defect.

[0097] The method for forming a pattern using the chemically amplified resist composition of the present application, since it can satisfy high resolution, a pattern formation with reduced LER, and can suppress a development residue defect, can be desirably used in fine processing technology, and in particular, can be desirably used in ArF, KrF, EUV, EB lithography, etc. DETAILED DESCRIPTION

[0098] As described above, development of a chemically amplified resist composition which satisfies good resolution, pattern shape, line edge roughness, and which can suppress development residue defects which become a cause of mask defects is required.

[0099] As a result of repeated and intensive studies to achieve the foregoing object, the present inventors have obtained the following insight: introduction of a high molecular compound having a repeating unit polymerized from a specific polymerizable monomer into a resist composition can satisfy good resolution, pattern shape, line edge roughness, and can suppress development residue defects which become a cause of mask defects, and thus the present application has been completed.

[0100] That is, the present application is a chemically amplified resist composition, comprising:

[0101] (A) a high molecular compound containing one or two or more kinds of repeating units, and at least one or more kinds of repeating units among the foregoing repeating units are repeating units polymerized from a polymerizable monomer having a residual oligomer of a dimer to a hexamer of 1000 ppm or less.

[0102] Hereinafter, the present application will be described in detail, but the present application is not limited thereto.

[0103] [Chemically amplified resist composition]

[0104] The resist composition of the present application is a chemically amplified resist composition, comprising:

[0105] (A) a high molecular compound containing one or two or more kinds of repeating units, and at least one or more kinds of repeating units among the foregoing repeating units are repeating units polymerized from a polymerizable monomer having a residual oligomer of a dimer to a hexamer of 1000 ppm or less.

[0106] [(A) High molecular compound]

[0107] In order to obtain the high molecular compound (A) used in the present application, in general, purification is performed with respect to a polymerizable monomer synthesized for the purpose of polymerizing a high molecular compound. The method of purification is not particularly limited, and can be performed using water washing, liquid separation, distillation, recrystallization, filtration, ultrafiltration, centrifugal separation, high performance liquid chromatography, column chromatography, and the like.

[0108] In the (A) component, in at least one kind of repeating unit, the residual oligomer of a dimer to a hexamer contained in the polymerizable monomer is 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, even more preferably 200 ppm or less, particularly preferably 100 ppm or less, and the oligomer is preferably controlled with respect to a dimer to a hexamer, and particularly preferably with respect to a dimer to a tetramer.

[0109] Further, as a stabilizer, a polymerization inhibitor such as TBC or BHT can be added as a stabilizer at the time of heating for solutionization at the time of use after purification, and at the time of long-term storage after purification.

[0110] When a polymer compound obtained by polymerizing a polymerizable monomer using only the above oligomer component exceeding 1000 ppm is used as a resist composition, there is a concern that a development residue defect can occur, and the yield, which is important for semiconductor manufacturing processes, can be reduced.

[0111] Further, the analysis of the residual oligomer can be performed using LC-MS.

[0112] (A) The proportion of repeating units in the polymer compound of the component (A) that are obtained by polymerizing a polymerizable monomer with a residual oligomer of 2 to 6-mers being 1000 ppm or less is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, yet more preferably 30 mol% or more, particularly preferably 40 mol% or more, and further preferably 80 mol% or more, and most preferably 100 mol% or more.

[0113] Further, among the one or two or more kinds of repeating units contained in the polymer compound of the component (A), it is arbitrary which kind of repeating unit is the repeating unit obtained by polymerizing a polymerizable monomer with a residual oligomer of 2 to 6-mers being 1000 ppm or less. That is, for example, any one of the repeating units contained in the polymer compound of the component (A) described later can be used.

[0114] As for the polymerizable monomer used in the present application, among polymerizable monomers having a mechanism in which an acid leaving group is triggered to cause an elimination reaction by the action of an acid generated by exposure, and becomes soluble to an alkali developer, or among polymerizable monomers having a mechanism in which an acid leaving group is triggered to cause an elimination reaction and becomes insoluble to an alkali developer, the residual oligomer of 2 to 6-mers contained therein is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, yet more preferably 200 ppm or less, particularly preferably 100 ppm or less, and further preferably, the oligomer is controlled to be an oligomer of 2 to 4-mers. The unit that is triggered to cause a reaction by the action of an acid generated by exposure has a large influence on defects in a resist composition, and therefore, the inhibition of the oligomer is important.

[0115] <Repeating Unit A1>

[0116] When the chemical amplification resist composition of the present application is a chemical amplification positive resist composition, it is preferable to include a repeating unit A1 represented by the following general formula (Al) with respect to a unit having a mechanism in which an acid leaving group causes an elimination reaction and becomes soluble to an alkali developer. Also, at this time, the aforementioned repeating unit A1 is preferably a repeating unit obtained by polymerizing a polymerizable monomer having a residual oligomer of 2 to 6 polymers of 1000 ppm or less.

[0117] [Chemical 13]

[0118]

[0119] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 12 are each independently a halogen atom, a linear or branched or cyclic acyloxy group having 2 to 8 carbons which can be substituted with a halogen, a linear or branched or cyclic alkyl group having 1 to 6 carbons which can be substituted with a halogen, or a linear or branched or cyclic alkoxy group having 1 to 6 carbons which can be substituted with a halogen. A 2 is a single bond, or a linear or branched or cyclic alkylene group having 1 to 11 carbons which can be inserted with an ether bond or an ester bond between carbon-carbon bonds. s is 0 or 1. t is an integer of 0 to 2. c is an integer satisfying 0 < c < 5 + 2t - e. d is 0 or 1. e is an integer of 1 to 3. r is 0 or 1. X is an acid-labile group when e is 1, and is a hydrogen atom or an acid-labile group when e is 2 or more, but at least one thereof is an acid-labile group.

[0120] The repeating unit A1 is one in which at least one of the phenolic hydroxyl groups bonded to the aromatic ring is protected by an acid-labile group, one in which the carboxyl group bonded to the aromatic ring is protected by an acid-labile group, or one in which the carboxyl group contained in the (meth)acrylate is protected by an acid-labile group. Such an acid-labile group, if it is one which is continuously removed by an acid and provides an acidic group in a variety of known chemical amplification resist compositions, can be used without particular limitation.

[0121] Among the repeating units contained in the high molecular compound of the (A) component of the present invention, the repeating unit represented by the above general formula (A1) that is the repeating unit having an acid-labile group in which the hydrogen atom of the phenolic hydroxyl group is substituted is preferably a repeating unit in which the hydrogen atom of the hydroxyl group of hydroxystyrene, hydroxylphenyl (meth) acrylate is substituted, and the monomer used to obtain this repeating unit can be exemplified by the monomers described in paragraph

[0029] of Japanese Patent Application Publication No. 2014-219657. The repeating unit represented by the above general formula (A1) that is the repeating unit having an acid-labile group in which d is 1 is preferably a repeating unit in which the hydrogen atom of the carboxyl group of (meth) acrylate is substituted, and the monomer used to obtain this repeating unit can be exemplified by the monomers described in paragraph

[0028] of Japanese Patent Application Publication No. 2014-219657.

[0122] The structure of the acid-labile group can also be exemplified by the monomers described in paragraphs

[0030] to

[0082] of Japanese Patent Application Publication No. 2014-219657. The ideal structure of the acid-labile group can be specifically exemplified by the formulae (H-3)-1 to (H-3)-19 shown below.

[0123] [Chemical Formula 14]

[0124]

[0125] In the formulae (H-3)-1 to (H-3)-19, R L43 represents the same or different saturated hydrocarbon group or aryl group such as phenyl having a carbon number of 6 to 20. R L44 , R L46 is a hydrogen atom or saturated hydrocarbon group having a carbon number of 1 to 20. R L45 represents aryl group such as phenyl having a carbon number of 6 to 20. The aforementioned saturated hydrocarbon group can be any one of linear, branched, or cyclic. Also, the aforementioned aryl group is preferably phenyl or the like. R F is a fluorine atom or trifluoromethyl group. n is an integer of 1 to 5.

[0126] When the aforementioned acid-labile group is a tertiary alkyl group, even when the resist film thickness is, for example, 10 to 100 nm and a fine pattern having a line width of 45 nm or less is formed, a pattern having a small LER is provided, and thus this is preferable. In the case of the aforementioned tertiary alkyl group, in order to obtain a monomer for polymerization by distillation, it is preferable that the carbon number be 4 to 18. Also, the alkyl substituent of the tertiary carbon of the aforementioned tertiary alkyl group can be exemplified by linear or branched or cyclic alkyl group having a carbon number of 1 to 20 that can also have an oxygen-containing functional group such as ether group, carbonyl group, and the alkyl substituents of the aforementioned tertiary carbon can also be bonded to each other and form a ring.

[0127] Specific examples of alkyl substituents on the aforementioned tertiary carbons include: methyl, ethyl, propyl, adamantyl, norbornel, tetrahydrofuran-2-yl, 7-oxanorborne-2-yl, cyclopentyl, 2-tetrahydrofuranyl, tricyclic [5.2.1.0] 2,6 ] decyl, tetracyclic [4.4.0.1 2,5 .1 7,10 Dodecyl, 3-oxo-1-cyclohexyl.

[0128] Furthermore, examples of tertiary alkyl groups having these as substituents include: tert-butyl, tert-pentyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1,2-trimethylpropyl, 1-adamantyl-1-methylethyl, 1-methyl-1-(2-norbornenyl)ethyl, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl, 1-methyl-1-(7-oxanorbornen-2-yl)ethyl, 1-methylcyclopentyl, 1-ethyl Cyclopentyl, 1-propylcyclopentyl, 1-isopropylcyclopentyl, 1-cyclopentylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(2-tetrahydrofuranyl)cyclopentyl, 1-(7-oxanorbornen-2-yl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-cyclopentylcyclohexyl, 1-cyclohexylcyclohexyl, 2-methyl-2-norbornenyl, 2-ethyl-2-norbornenyl, 8-methyl-8-tricyclo[5.2.1.0] 2,6 ] Decyl, 8-ethyl-8-tricyclo[5.2.1.0 2,6 Decyl, 3-methyl-3-tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl, 3-ethyl-3-tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 2-isopropyl-2-adamantyl, 1-methyl-3-oxo-1-cyclohexyl, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl, 5-hydroxy-2-methyl-2-adamantyl, 5-hydroxy-2-ethyl-2-adamantyl, etc., are preferably in the form of the structures shown below.

[0129] [Chemistry 15]

[0130]

[0131] [Chemistry 16]

[0132]

[0133] [Chemistry 17]

[0134]

[0135] [Chemistry 18]

[0136]

[0137] Further, an acetal group represented by the following general formula (B2-1) is often used as an acid-labile group, and is a useful option as an acid-labile group that stably provides a pattern with a more rectangular interface with a substrate.

[0138] [Chemical Formula 19]

[0139]

[0140] In the formula, R 16 is a hydrogen atom, or a linear or branched or cyclic alkyl group having 1 to 10 carbons. Y is a linear or branched or cyclic alkyl group having 1 to 30 carbons.

[0141] R 16 is appropriately selected in accordance with the design sensitivity to the acid-decomposable group. For example, if the design is to decompose with a strong acid after ensuring high stability, a hydrogen atom is selected, and if the design is to be highly sensitive to pH changes using high reactivity, a linear alkyl group is selected. Although it also depends on the combination of the acid generator and the basic compound incorporated in the resist composition, when the terminal is designed to be substituted with a larger alkyl group and the solubility change due to decomposition is large, R 16 is preferably a secondary carbon having a bond with the acetal carbon. R 16 Examples of R

[0142] Among the aforementioned acetal groups, in order to obtain higher resolution, Y is preferably a polycyclic alkyl group having 7 to 30 carbons. Further, when Y is a polycyclic alkyl group, it is preferable to form a bond between the secondary carbon constituting the polycyclic structure and the acetal oxygen. When the bond is formed on the secondary carbon of the ring structure, the polymer becomes a stable compound compared to when the bond is formed on the tertiary carbon, and the storage stability of the resist composition is good, and the resolution does not deteriorate. Further, compared to when Y forms a bond on the primary carbon into which a linear alkyl group having 1 or more carbons is inserted, the glass transition temperature (Tg) of the polymer when the bond is formed on the secondary carbon of the ring structure is good, and the resist pattern after development does not cause shape defects due to baking.

[0143] Ideal examples of the acetal group represented by the general formula (B2-1) can be exemplified by the following, but are not limited thereto. In the following formula, R 16 is the same as the aforementioned.

[0144] [Chemical Formula 20]

[0145]

[0146] The repeating unit A1 is preferably introduced in a range of 5 to 70 mol% relative to the total repeating units of the high molecular compound of the component (A), and more preferably in a range of 5 to 60 mol%.

[0147] <Repeating unit A2>

[0148] When the chemically amplified resist composition of the present application is a chemically amplified negative resist composition, it preferably contains a repeating unit A2 represented by the following general formula (A2) as a unit having an acid leaving group that induces an elimination reaction and a mechanism of becoming insoluble to an alkali developer by the action of an acid generated from an acid generator. Also, at this time, the aforementioned repeating unit A2 is preferably a repeating unit obtained by polymerizing a polymerizable monomer having a residual oligomer of 2 to 6 polymers at 1000 ppm or less.

[0149] [Chemical 21]

[0150]

[0151] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. A 1 is a single bond, or a saturated hydrocarbylene group having 1 to 10 carbon atoms, and -CH2- constituting the saturated hydrocarbylene group can be substituted with -O-. R 1 are each independently a halogen atom, a saturated hydrocarbylcarbonyloxy group having 2 to 8 carbon atoms which can be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which can be substituted with a halogen atom, or a saturated hydrocarbyloxy group having 1 to 6 carbon atoms which can be substituted with a halogen atom. W 1 is a hydrogen atom, or an aliphatic hydrocarbyl group having 1 to 10 carbon atoms, or an aryl group which can have a substituent, and -CH2- constituting the aliphatic hydrocarbyl group can be substituted with -O-, -C(=O)-, -O-C(=O)- or -C(=O)-O-. Rx and Ry are each independently a hydrogen atom, a saturated hydrocarbyl group having 1 to 15 carbon atoms which can be substituted with a hydroxyl group or a saturated hydrocarbyloxy group, or an aryl group which can have a substituent. However, Rx and Ry are not simultaneously a hydrogen atom. Also, Rx and Ry can be bonded to each other and form a ring together with the carbon atom to which they are bonded. y is an integer of 0 to 2. u is 0 or 1. f is an integer satisfying 0 ≤ f ≤ 5 + 2y - g. g is an integer of 1 to 3.

[0152] The repeating unit A2 is a repeating unit that, upon irradiation with high-energy rays, induces an elimination reaction of the acid dissociable group by the action of an acid generated from an acid generator, and induces alkali insolubilization and cross-linking reaction between polymers. By the action of the repeating unit A2, the negative conversion reaction can be more efficiently performed, and thus the resolution performance can be improved.

[0153] W 1An aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group which can also have a substituent (aliphatic 1-valent hydrocarbon group or 1-valent aromatic ring group) can be exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a methylcarbonyl group, a phenyl group, and the like.

[0154] Rxor Rydesirably can be exemplified by a methyl group, an ethyl group, a propyl group, a butyl group, structural isomers thereof, or a moiety of the hydrogen atoms thereof being replaced with a hydroxyl group or an alkoxy group.

[0155] y is an integer of 0 to 2, is a benzene ring when 0, is a naphthalene ring when 1, and is an anthracene ring when 2.

[0156] A 1 Examples of the alkylene group represented by the formula can be exemplified by a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and structural isomers having a branched or cyclic structure of the carbon skeleton, and the like. In the case where the aforementioned alkylene group contains an ether bond, when u in the general formula (A2) is 1, a second ether bond can be inserted at any position other than between the carbon in the α position and the carbon in the β position with respect to the ester oxygen. Also, when u is 0, the atom bonded to the main chain can also be an ether bond, and a second ether bond can be inserted at any position other than between the carbon in the α position and the carbon in the β position with respect to the ether bond.

[0157] The repeating unit A2 is desirably a repeating unit represented by the following general formula (A2-1), (A2-2).

[0158] [Chemical Formula 22]

[0159]

[0160] In the formula, R A , Rx, Ry, and g are the same as described above.

[0161] Desirable examples of the repeating unit A2 can be exemplified by the following, but are not limited thereto. In the following examples, Me is a methyl group, and Ac is an acetyl group.

[0162] [Chemical Formula 23]

[0163]

[0164] [Chemical Formula 24]

[0165]

[0166] [Chemical Formula 25]

[0167]

[0168] [Chemical Formula 26]

[0169]

[0170] [Chemical Formula 27]

[0171]

[0172] The content of the repeating unit A2 is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, and is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, in the total repeating units of the high molecular compound constituting the component (A).

[0173] <Repeating unit A3>

[0174] The high molecular compound of the component (A) used in the chemically amplified resist composition of the present application preferably further contains a repeating unit A3 represented by the following general formula (A3).

[0175] [Chemical 28]

[0176]

[0177] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R 11 are each independently a halogen atom, a carbons number 2 to 8 saturated hydrocarbylcarbonyloxy group which can be substituted by a halogen atom, a carbons number 1 to 6 saturated hydrocarbyl group which can be substituted by a halogen atom, or a carbons number 1 to 6 saturated hydrocarbyloxy group which can be substituted by a halogen atom. A 1 is a single bond or a carbons number 1 to 10 saturated hydrocarbylene group, and -CH2- constituting the saturated hydrocarbylene group can be substituted by -O-. s is 0 or 1. w is an integer of 0 to 2. a is an integer satisfying 0 ≤ a ≤ 5 + 2w - b. b is an integer of 1 to 3.

[0178] when the linking group (-CO-O-A 1 -) is not present (i.e., in the general formula (A3), s is 0 and A 1 is a single bond), ideal examples of the repeating unit A3 can include units derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, and the like. Among them, those represented by the following general formula (A3-1) are more preferable.

[0179] [Chemical 29]

[0180]

[0181] In the formula, R A and b are the same as described above.

[0182] when the linking group (-CO-O-A 1 -) is present, ideal examples of the repeating unit A3 can include, but are not limited to, those shown below.

[0183] [Chemical 30]

[0184]

[0185] The repeating unit A3 can be used singly or in combination. Of all the repeating units of the aforementioned high molecular compound of the component (A), the repeating unit A3 is preferably introduced in a range of 10 to 95 mol%, and more preferably in a range of 30 to 85 mol%. However, when at least one or more of the repeating units represented by the general formula (A12) and the general formula (A13) described later, which are used in the present application to impart a higher etching resistance to the polymer, are contained and the units have a phenolic hydroxyl group as a substituent, the ratio thereof is preferably adjusted to be within the aforementioned range.

[0186] <Repeating units A4 to A11>

[0187] The chemically amplified resist composition of the present application can further contain at least one of the repeating units represented by the general formulae (A4) to (A11) described below.

[0188] [Chemical formula 31]

[0189]

[0190] In the formula, R B are each independently a hydrogen atom or a methyl group. Z 1 is a single bond, an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, -O-Z 11 -, -C(=O)-O-Z 11 -, or -C(=O)-NH-Z 11 , Z 11 is an aliphatic hydrocarbylene group having a carbon number of 1 to 6, or a phenylene group, a naphthylene group, or a group having a carbon number of 7 to 18 obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 2 is a single bond or -Z 21 -C(=O)-O-, Z 21 is a hydrocarbylene group having a carbon number of 1 to 20, which can also contain a hetero atom. Z 3 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -O-Z 31 -, -C(=O)-O-Z 31 -, or -C(=O)-NH-Z 31 , Z 31 is an aliphatic hydrocarbylene group having a carbon number of 1 to 6, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, or a group having a carbon number of 7 to 20 obtained by combining them, and can also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. Z 4 is a single bond or a hydrocarbylene group having a carbon number of 1 to 30, which can also contain a hetero atom. k 1 and k2 Each can be independently 0 or 1, but Z 4 When it is a single bond, k 1 and k 2 It is 0. R 21 ~R 38 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms. Also, R 21 and R 22 They can also bond to each other and form rings together with the sulfur atoms they are bonded to, and R 23 and R 24 R 26 and R 27 or R 29 and R 30 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. R HF It can be a hydrogen atom or a trifluoromethyl group. Xa - It is a non-nucleophilic relative ion.

[0191] In general formulas (A5, A9), Z 2 -Z 21 When -C(=O)-O-, Z 21 The following are examples of alkylene groups (divalent hydrocarbon groups) containing 1 to 20 carbon atoms that may also contain heteroatoms, but are not limited to these.

[0192] [Chemistry 32]

[0193]

[0194] In the formula, the dashed line represents an atomic bond.

[0195] In repeating units A4 and A8, Xa - Examples of non-nucleophilic relative ions can be cited in Japanese Patent Application Publication Nos. 2010-113209 and 2007-145797. Furthermore, in repeating units A5 and A9, R... HF Specific examples of the form being a hydrogen atom can be cited in Japanese Patent Application Publication No. 2010-116550, R. HF Specific examples of trifluoromethyl can be found in Japanese Patent Application Publication No. 2010-77404. Repeating units A6 and A10 can be found in Japanese Patent Application Publication Nos. 2012-246265 and 2012-246426.

[0196] Ideal examples of monomers providing repeating units A7 and A11 anionic sites are listed below, but are not limited thereto.

[0197] [Chemistry 33]

[0198]

[0199] [Chemistry 34]

[0200]

[0201] In general formulas (A4) to (A11), R 21 ~R 38 Each hydrocarbon group can be independently composed of 1 to 20 carbon atoms and may also contain heteroatoms. The aforementioned hydrocarbon group can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples are similar to those illustrated in paragraphs

[0022] and

[0023] of Japanese Patent Application Publication No. 2010-116550. Furthermore, some or all of the hydrogen atoms in the aforementioned hydrocarbon group can be replaced by groups containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms. Groups containing heteroatoms such as oxygen, sulfur, or nitrogen atoms can also be inserted between the carbon-carbon bonds of the aforementioned hydrocarbon group. As a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sulfonyl lactone rings, carboxylic anhydrides, haloalkyl groups, etc.

[0202] Also, R 21 and R 22 They can also bond to each other and form rings together with the sulfur atoms they are bonded to, and R 23 and R 24 R 26 and R 27 、or R 29 and R 30 They can also bond to each other and form rings together with the sulfur atoms they are bonded to. Examples of such rings are shown below.

[0203] [Chemistry 35]

[0204]

[0205] In the formula, R 32 and R 21 ~R 38 The groups represented are the same.

[0206] The specific structures of sulfonium cations in general formulas (A5) to (A7) can be listed below, but are not limited thereto.

[0207] [Chemistry 36]

[0208]

[0209] [Chemistry 37]

[0210]

[0211] [Chemistry 38]

[0212]

[0213] [Chem. 39]

[0214]

[0215] [Chem. 40]

[0216]

[0217] [Chem. 41]

[0218]

[0219] [Chem. 42]

[0220]

[0221] [Chem. 43]

[0222]

[0223] [Chem. 44]

[0224]

[0225] [Chem. 45]

[0226]

[0227] [Chem. 46]

[0228]

[0229] [Chem. 47]

[0230]

[0231] [Chem. 48]

[0232]

[0233] [Chem. 49]

[0234]

[0235] [Chem. 50]

[0236]

[0237] [Chem. 51]

[0238]

[0239] [Chem. 52]

[0240]

[0241] [Chemical Formula 53]

[0242]

[0243] Specific structures of the picryl cation in General Formula (A9) to (A11) can include, but are not limited to, those shown below.

[0244] [Chemical Formula 54]

[0245]

[0246] The repeating units A4 to A11 are units that generate acid by irradiation with high-energy rays. It is thought that by containing these units in the polymer, acid diffusion can be moderately inhibited, and a pattern with reduced LER can be obtained. Also, it is thought that by containing these units in the polymer, at the time of baking in a vacuum, the phenomenon of acid volatilization from the exposed portion and reattachment to the unexposed portion is inhibited, and reduction in LER, reduction in defects due to undesirable negative tone reaction of the unexposed portion if negative type, and the like are effective, and reduction in shape degradation due to film loss if positive type, and the like are effective. The content of the repeating units A4 to A11 is preferably 0.1 to 30 mol%, and more preferably 0.5 to 20 mol% in the total repeating units constituting the aforementioned high molecular compound.

[0247] <Repeating Units A12 to A14>

[0248] The aforementioned high molecular compound of the (A) component can also contain at least one of the repeating units A12 to A14 represented by General Formulae (A12) to (A14) below in order to improve etching resistance.

[0249] [Chemical Formula 55]

[0250]

[0251] In the formula, R A is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 13 and R 14 are each independently a hydroxyl group, a halogen atom, an acetoxy group, a linear or branched or cyclic acyloxy group having 2 to 8 carbons which can be substituted with a halogen, a linear or branched or cyclic alkyl group having 1 to 8 carbons which can be substituted with a halogen, a linear or branched or cyclic alkoxy group having 1 to 8 carbons which can be substituted with a halogen, or a linear or branched or cyclic alkylcarbonyloxy group having 2 to 8 carbons which can be substituted with a halogen. R 15acyloxy group, a linear or branched or cyclic alkyl group having 1 to 20 carbons, a linear or branched or cyclic alkoxy group having 1 to 20 carbons, a linear or branched or cyclic acyloxy group having 2 to 20 carbons, a linear or branched or cyclic alkoxyalkyl group having 2 to 20 carbons, an alkylthioalkyl group having 2 to 20 carbons, a halogen atom, a nitro group, a cyano group, a sulfinyl group, or a sulfonyl group.A 3 is a single bond, or a linear or branched or cyclic alkylene group having 1 to 10 carbons, and an ether bond can also be inserted between carbon-carbon bonds. o and p are each independently an integer of 0 to 4. h is an integer of 0 or 1. j is an integer of 0 to 5. k is an integer of 0 to 2.

[0252] A 3 Examples of the alkylene group represented by the above formula (Al 4) can include methylene, ethylene, propylene, butylene, pentylene, hexylene, and structural isomers having a branched or cyclic carbon skeleton. In the case where the above alkylene group contains an ether bond, when h in the general formula (Al 4) is 1, a second ether bond can be inserted at any position other than between the carbon in the α position and the carbon in the β position with respect to the ester oxygen. Also, when h is 0, the atom to which the main chain is bonded can also be an ether oxygen, and a second ether bond can be inserted at any position other than between the carbon in the α position and the carbon in the β position with respect to the ether oxygen. In addition, when the above alkylene group has 10 or fewer carbons, it is desirable because solubility in an alkali developer can be sufficiently obtained.

[0253] Examples of R 15 include a chlorine atom, a bromine atom, an iodine atom; an alkyl group including a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and structural isomers thereof, a cyclopentyl group, a cyclohexyl group; an alkoxy group including a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, and structural isomers of the hydrocarbon portion thereof, a cyclopentyl-oxy group, a cyclohexyl-oxy group, and the like. Among them, a methoxy group and an ethoxy group are particularly effective. Also, an acyloxy group can be easily introduced by a chemical modification method even after polymerization of the polymer, and can be advantageously used for fine adjustment of solubility in an alkali developer of the base polymer. Examples of the above acyloxy group include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a pentylcarbonyloxy group, a hexylcarbonyloxy group, and structural isomers thereof, a cyclopentylcarbonyloxy group, a cyclohexylcarbonyloxy group, a benzoyloxy group, and the like. When the number of carbons is 20 or less, it is possible to appropriately set the effect (mainly a reduction effect) of controlling and adjusting solubility in an alkali developer of the base resin, and it is possible to suppress occurrence of scum. Also, among the above desirable substituents, substituents that are particularly easy to prepare in monomer form and can be effectively used can include a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a methoxy group.

[0254] In General Formula (A14), k is an integer of 0 to 2, and represents a benzene skeleton when k is 0, a naphthalene skeleton when k is 1, and an anthracene skeleton when k is 2. When k is 0, j is preferably an integer of 0 to 3, and when k is 1 or 2, j is preferably an integer of 0 to 4.

[0255] h is 0 and A 3 When h is 0, that is, the aromatic ring is directly bonded to the main chain of the high molecular compound, that is, without a linking group, ideal examples of the repeating unit A14 can be exemplified by units derived from styrene, 4-chlorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-bromostyrene, 4-acetoxy styrene, 2-hydroxypropylstyrene, 2-vinylnaphthalene, 3-vinylnaphthalene, and the like.

[0256] Further, when h is 1, that is, a linking group having an ester skeleton is present, ideal examples of the repeating unit A14 can be exemplified by, but not limited to, the following.

[0257] [Chemical Formula 56]

[0258]

[0259] [Chemical Formula 57]

[0260]

[0261] When at least one of the repeating units A12 to A14 is used as a constituting unit, etching resistance of the aromatic ring can be obtained, and the effect of improving electron beam irradiation resistance at the time of etching and pattern inspection due to the addition of a ring structure to the main chain can also be obtained.

[0262] The repeating units A12 to A14 can be used alone or in combination of two or more. In order to obtain the effect of improving etching resistance, the content of the repeating units A12 to A14 is preferably 2 mol% or more, more preferably 5 mol% or more, and is preferably 35 mol% or less, more preferably 20 mol% or less, in the total repeating units of the aforementioned high molecular compound constituting the (A) component.

[0263] <Repeating Unit of (Meth)Acrylate Having a Close Contact Group>

[0264] The aforementioned high molecular compound of the (A) component can also contain a repeating unit of a (meth)acrylate having a close contact group such as a lactone structure, a hydroxyl group other than a phenolic hydroxyl group, or other repeating units in order to perform fine adjustment of the properties of the resist film. Examples of the aforementioned repeating unit of a (meth)acrylate having a close contact group can be exemplified by units represented by the following Formulae (bl) to (b3).

[0265] [Chemical Formula 58]

[0266]

[0267] wherein R A and the foregoing. J 1 is -O- or methylene. J 2 is a hydrogen atom or a hydroxyl group. J 3 is a linear or branched or cyclic alkyl group having 1 to 4 carbon atoms. n is an integer of 0 to 3.

[0268] These units do not exhibit acidity and can be used as units that provide adhesion to a substrate, units that adjust solubility, and the like, in an auxiliary manner.

[0269] When the aforementioned high molecular compound of the component (A) does not contain the repeating units A4 to A11, the content of the repeating unit A3 in the high molecular compound is preferably 25 to 95 mol%, more preferably 40 to 85 mol%. The content of the repeating units A12 to A14 is preferably 0 to 30 mol%, more preferably 3 to 20 mol%. The content of the repeating unit A1 or A2 is preferably 5 to 70 mol%, more preferably 5 to 60 mol%. In addition, other repeating units can be contained in an amount of 0 to 30 mol%, preferably 0 to 20 mol%.

[0270] When the aforementioned high molecular compound of the component (A) contains the repeating units A4 to A11, the content of the repeating unit A3 in the high molecular compound is preferably 25 to 94.5 mol%, more preferably 36 to 85 mol%. The content of the repeating units A12 to A14 is preferably 0 to 30 mol%, more preferably 3 to 20 mol%. The content of the repeating unit A1 or A2 is preferably 5 to 70 mol%, more preferably 5 to 60 mol%. In addition, the total content of the repeating units A1 or A2, A12, A13, and A14 is preferably 60 to 99.5 mol%. The content of the repeating units A4 to A11 is preferably 0.5 to 20 mol%, more preferably 1 to 10 mol%. In addition, other repeating units can be contained in an amount of 0 to 30 mol%, preferably 0 to 20 mol%.

[0271] When a positive resist is formed, the aforementioned high molecular compound of the component (A) is preferably one that contains the repeating unit represented by the following general formula (A1-1), the repeating unit represented by the following general formula (A3-1), and the repeating unit represented by the following general formula (A7-1).

[0272] [Chemical Formula 59]

[0273]

[0274] wherein R A , R B , Z 4 , R 29 , R 30 , R 31 , and b are the same as the foregoing. R 50 is an acid-labile group.

[0275] Further, in the case of constructing a positive resist, the aforementioned high molecular compound of the component (A) is preferably a high molecular compound containing the repeating unit A1 represented by the aforementioned general formula (Al) and the repeating unit A3 represented by the aforementioned general formula (A3) and not containing the repeating units A4 to Al l represented by the aforementioned general formulae (A4) to (Al l).

[0276] Further, in the case of constructing a negative resist, the aforementioned high molecular compound of the component (A) is preferably a high molecular compound containing the repeating unit represented by the aforementioned general formula (A2-1) or the aforementioned general formula (A2-2), the repeating unit represented by the aforementioned general formula (A3-1), and the repeating unit represented by the aforementioned general formula (A5-1).

[0277] [Chemical Formula 60]

[0278]

[0279] in the formula, R A , R B , Z 2 , R 23 , R 24 , R 25 , Rx, Ry, b, and g are the same as described above.

[0280] Further, in the case of constructing a negative resist, the aforementioned high molecular compound of the component (A) is preferably a high molecular compound containing the repeating unit A2 represented by the aforementioned general formula (A2) and the repeating unit A3 represented by the aforementioned general formula (A3) and not containing the repeating units A4 to Al l represented by the aforementioned general formulae (A4) to (Al l).

[0281] The aforementioned high molecular compound of the component (A) can also be used in combination of a polymer not containing the repeating units A4 to Al l and a polymer containing the repeating units A4 to Al l. In this case, the blending amount of the polymer not containing the repeating units A4 to Al l is preferably 2 to 5,000 parts by mass and more preferably 10 to 1,000 parts by mass with respect to 100 parts by mass of the polymer containing the repeating units A4 to Al l.

[0282] Further, in the case where the high molecular compound of the component (A) used in the present application is a polymer of two or more polymerizable monomers, the total of the residual oligomers of the 2- to 6-mer contained in all the polymerizable monomers used is preferably 5,000 ppm or less and more preferably 3,000 ppm or less, and control is preferably performed with respect to the oligomers of the 2- to 4-mer. When the residual oligomers of the 2- to 6-mer contained in all the polymerizable monomers are 5,000 ppm or less, it is possible to more reliably prevent the occurrence of development residue defects and to cause a decrease in yield, which is important for semiconductor manufacturing processes.

[0283] Of all the repeating units of the aforementioned high molecular compound constituting the (A) component, it is desirable that repeating units A1 to A14 account for 70 mol% or more, and more desirably 80 mol% or more. By doing so, it is possible to surely obtain the properties necessary for the chemical amplification resist composition of the present application used particularly for manufacturing a photomask substrate.

[0284] When the positive resist composition is used for photomask manufacturing, the coating film thickness in the most advanced era is 150 nm or less, and desirably 100 nm or less. In terms of the design of the base polymer constituting the aforementioned positive resist composition, the dissolution rate to an alkali developer is 8 nm / min or less, desirably 6 nm / min or less, and more desirably 5 nm / min or less. In the advanced era, when the coating film applied to a substrate falls within the thin film region (100 nm or less), the influence of the loss of the pattern film to alkali development becomes large, and when the alkali dissolution rate of the polymer is greater than 8 nm / min, the pattern collapses, and a fine pattern cannot be formed. Particularly, in the case of photomask manufacturing where defects are not allowed, there is a tendency to perform strong development processing, and thus this is significant. In addition, in the present application, the dissolution rate of the base polymer to an alkali developer is a value calculated from the amount of film loss when a polymer solution is spin-coated on a silicon wafer having a diameter of 200 mm (8 inches) and baked at 100°C for 90 seconds, and then developed with a 2.38% aqueous TMAH solution for 100 seconds.

[0285] Also, when the negative resist composition is used for photomask manufacturing, the coating film thickness in the most advanced era is 150 nm or less, and desirably 100 nm or less. The dissolution rate of the base polymer constituting the aforementioned negative resist composition to an alkali developer (2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution) is, in general, in the case of strong development processing for the purpose of reducing defects caused by resist residues, and desirably 80 nm / sec or less, and more desirably 50 nm / sec or less for the purpose of forming a fine pattern. Also, for example, when the negative resist composition of the present application is used in an EUV exposure process for manufacturing an LSI wafer from a wafer, since it is necessary to pattern a fine line of 50 nm or less, the coating film thickness is often adjusted to 100 nm or less, and from the viewpoint of considering the deterioration of the pattern caused by development in the case of a thin film, the dissolution rate of the polymer used desirably is 80 nm / sec or less, and more desirably 50 nm / sec or less. On the other hand, in a KrF exposure process, although it also depends on the purpose, the coating film thickness is often a thick film of 200 nm or more, and in this case, the dissolution rate of the polymer used desirably is designed to be 90 nm / sec or more.

[0286] The aforementioned high molecular compound of the component (A) can be synthesized by copolymerizing each monomer after protecting the respective monomers with a protecting group as needed using a publicly known method, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited, and is preferably radical polymerization, anionic polymerization. For these methods, refer to International Publication No. 2006 / 121096, Japanese Patent Application Publication No. 2008-102383, Japanese Patent Application Publication No. 2008-304590, and Japanese Patent Application Publication No. 2004-115630.

[0287] The weight average molecular weight (Mw) of the aforementioned high molecular compound of the component (A) is preferably 1,000 to 50,000, and more preferably 2,000 to 25,000. If the Mw is 1,000 or more, there is no concern that phenomena such as rounding of the head of the pattern, reduction in resolution, and LER degradation will occur as known in the past. On the other hand, if the Mw is 50,000 or less, there is no concern that LER will increase, particularly when forming a pattern with a line width of 100 nm or less. In addition, in the present application, the Mw is a polystyrene conversion value measured by gel permeation chromatography (GPC).

[0288] The molecular weight distribution (Mw / Mn) of the aforementioned high molecular compound of the component (A) is preferably 1.0 to 2.5, and more preferably 1.0 to 2.2, which is narrow dispersion. When the distribution is thus narrow, there is no concern that foreign matter will be generated on the pattern after development, or that the shape of the pattern will deteriorate.

[0289] [(B) Acid Generator]

[0290] The chemically amplified resist composition of the present application can also contain a (B) acid generator, particularly a photoacid generator, in order to function as a chemically amplified resist composition. The photoacid generator, if it is a compound that generates an acid by irradiation of high energy rays, is not particularly limited. Ideal photoacid generators are sulfonium salts, iodonium salts, sulfonyl diazomethane, N-sulfonyloxy imide, oxime-O-sulfonic acid ester type acid generators, and the like. One kind can be used alone, or two or more kinds can be used in combination.

[0291] Specific examples of the photoacid generator can include: nonafluorobutanesulfonate, partially fluorinated sulfonate salts described in paragraphs

[0247] to

[0251] of Japanese Patent Application Publication No. 2012-189977, partially fluorinated sulfonate salts described in paragraphs

[0261] to

[0265] of Japanese Patent Application Publication No. 2013-101271, and those described in paragraphs

[0122] to

[0142] of Japanese Patent Application Publication No. 2008-111103, paragraphs

[0080] to

[0081] of Japanese Patent Application Publication No. 2010-215608, and the like. Among the foregoing specific examples, the photoacid generator of the arylsulfonate type or the alkylsulfonate type is more desirable because it generates an acid of a strength suitable for deprotecting the acid-labile group of the repeating unit represented by General Formula (A1). Such a photoacid generator is preferably a compound having a sulfonium anion having the structure shown below. The paired cation can be exemplified by the foregoing specific examples of the sulfonium cation in General Formulas (A5) to (A7).

[0292] [Chem. 61]

[0293]

[0294] [Chem. 62]

[0295]

[0296] [Chem. 63]

[0297]

[0298] [Chem. 64]

[0299]

[0300] [Chem. 65]

[0301]

[0302] [Chem. 66]

[0303]

[0304] [Chem. 67]

[0305]

[0306] (B) The content of the acid generator, especially the photoacid generator, is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, relative to 80 parts by mass of the high-molecular compound of the component (A). The acid strength of the desired anion is preferably -1.5 or more. The pKa value is calculated using the pKa DB in ACD / Chemsketch ver: 9.04 by Advanced Chemistry Development, Inc.

[0307] [(C) Basic compound (quencher)]

[0308] The chemical amplification resist composition of the present application preferably contains a basic compound. The most suitable basic compound can be exemplified by known basic compounds.

[0309] The known basic compounds can be exemplified by primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates, and the like. In particular, the primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Application Publication No. 2008-111103, the amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, a sulfonate bond, or the like, and the compounds having a carbamate group described in Japanese Patent No. 3790649, and the like are particularly preferable. The desired basic compounds can be exemplified by tris[2-(methoxymethoxy)ethyl]amine, tris[2-(methoxymethoxy)ethyl]amine N-oxide, dibutylaminobenzoic acid, morpholine derivatives, imidazole derivatives, and the like. By adding such a basic compound, for example, the diffusion speed of the acid in the resist film can be more inhibited or the shape can be corrected.

[0310] Further, the aforementioned quencher can be exemplified by the sulfonium salt, iodonium salt, ammonium salt, or the like of the carboxylic acid having no fluorine at the α position described in Japanese Patent Application Publication No. 2008-158339. The sulfonic acid, imide acid, or methylate acid having fluorine at the α position is necessary for deprotection of the acid-labile group, and by salt exchange with the salt of the onium salt having no fluorine at the α position, the carboxylic acid having no fluorine at the α position is released. The carboxylic acid having no fluorine at the α position hardly causes the deprotection reaction, and thus functions as a quencher.

[0311] The onium salt of the carboxylic acid having no fluorine at the α position can be exemplified by a compound represented by the following general formula (H1).

[0312] [Chem. 68]

[0313]

[0314] In the general formula (H1), R101 a hydrocarbon group having 1 to 40 carbon atoms which can also contain heteroatoms, but excluding the case where the hydrogen atom of the carbon atom in the α-position to the sulfo group is replaced with a fluorine atom or a fluoroalkyl group.

[0315] The aforementioned hydrocarbon group can be saturated or unsaturated, and can be any of linear, branched, or cyclic. Specific examples thereof include: alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, t-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and the like; cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.02'6]decyl, adamantyl, adamantylmethyl, and the like; alkenyl groups such as vinyl, allyl, propenyl, butenyl, hexenyl, and the like; cyclic unsaturated aliphatic hydrocarbon groups such as cyclohexenyl, and the like; aryl groups such as phenyl, naphthyl, alkylphenyl (2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-t-butylphenyl, 4-n-butylphenyl, and the like), dialkylphenyl (2,4-dimethylphenyl, and the like), trialkylphenyl (2,4,6-triisopropylphenyl, and the like), alkylnaphthyl (methylnaphthyl, ethylnaphthyl, and the like), dialkylnaphthyl (dimethylnaphthyl, diethylnaphthyl, and the like), and the like; aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, and the like. 2,6

[0316] Further, a part of the hydrogen atoms of these groups can also be replaced with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, and the like, and a part of the carbon atoms of these groups can also be replaced with groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and the like, as a result of which hydroxyl groups, cyano groups, carbonyl groups, ether bonds, thioether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydrides, haloalkyl groups, and the like can also be contained. Hydrocarbon groups containing heteroatoms can include: heteroaryl groups such as thienyl, and the like; alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-t-butoxyphenyl, 3-t-butoxyphenyl, and the like; alkylnaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, n-butoxynaphthyl, and the like; dialkylnaphthyl groups such as dimethoxynaphthyl, diethoxynaphthyl, and the like; aralkyloxyalkyl groups such as 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, 2-(2-naphthyl)-2-oxoethyl, and the like; and the like.

[0317] In General Formula (H1), Mq + ​is a sulfonium cation, a sulfoxonium cation or an ammonium cation, more preferably a sulfonium cation or a sulfoxonium cation. Specific examples of the sulfonium cation in the above general formulae (A5) to (A7) can be desirably exemplified. Specific examples of the anion structure of the salt represented by the above general formula (H1) are exemplified below, but the present application is not limited thereto.

[0318] [Chemical Formula 69]

[0319]

[0320] [Chemical Formula 70]

[0321]

[0322] A sulfonium salt of a carboxylic acid containing an iodinated benzene ring represented by the following general formula (H2) can be desirably used as a quencher.

[0323] [Chemical Formula 71]

[0324]

[0325] In the general formula (H2), R 201 one or more of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an amino group, a nitro group, a cyano group, or a hydrogen atom can be substituted with a halogen atom, a saturated hydrocarbon group having a carbon number of 1 to 6, a saturated hydrocarbon group oxy group having a carbon number of 1 to 6, a saturated hydrocarbon group carbonyl oxy group having a carbon number of 2 to 6, or a saturated hydrocarbon group sulfonyl oxy group having a carbon number of 1 to 4, or -NR 201A -C(=O)-R 201B or -NR 201A -C(=O)-O-R 201B . R 201A is a hydrogen atom or a saturated hydrocarbon group having a carbon number of 1 to 6. R 201B is a saturated hydrocarbon group having a carbon number of 1 to 6 or an unsaturated aliphatic hydrocarbon group having a carbon number of 2 to 8.

[0326] In the general formula (H2), x is an integer of 1 to 5. y is an integer of 0 to 3. z is an integer of 1 to 3. L 1 is a single bond or a (z+1)-valent linking group having a carbon number of 1 to 20, and can also contain at least one selected from an ether bond, a carbonyl group, an ester bond, an amide bond, a sultone ring, a lactam ring, a carbonate group, a halogen atom, a hydroxyl group, and a carboxyl group. The above-mentioned saturated hydrocarbon group, saturated hydrocarbon group oxy group, saturated hydrocarbon group carbonyl oxy group, and saturated hydrocarbon group sulfonyl oxy group can be any one of linear, branched, or cyclic. When y and / or z is 2 or more, each R 201 may be the same as or different from each other.

[0327] In the general formula (H2), R 202 , R 203 , and R 204each independently is a halogen atom or a hydrocarbon group having a carbon number of 1 to 20 which can also contain a heteroatom. The aforementioned hydrocarbon group can be either saturated or unsaturated, and can be any of linear, branched, or cyclic. Specific examples thereof can include an alkyl group having a carbon number of 1 to 20, an alkenyl group having a carbon number of 2 to 20, an aryl group having a carbon number of 6 to 20, an aralkyl group having a carbon number of 7 to 20, and the like. Also, a part or all of the hydrogen atoms of these groups can be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, a nitro group, a sultone group, a sulfone group, or a group containing a sulfonium salt, and a part of the carbon atoms of these groups can be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate ester group, or a sulfonate ester bond. Also, R 202 and R 203 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

[0328] Specific examples of the compound represented by General Formula (H2) can include those described in Japanese Patent Application Publication No. 2017-219836. It is also high in absorption and high in sensitization effect, and is also high in acid diffusion control effect.

[0329] Also, the aforementioned quencher can also use a carboxylic acid salt type compound containing a nitrogen atom described in Japanese Patent Application Publication No. 2016-200805. Specific examples thereof can include those shown below, but are not limited thereto.

[0330] [Chemical Formula 72]

[0331]

[0332] [Chemical Formula 73]

[0333]

[0334] [Chemical Formula 74]

[0335]

[0336] [Chemical Formula 75]

[0337]

[0338] [Chemical Formula 76]

[0339]

[0340] Also, a betaine type compound of a weak acid can also be used as the aforementioned quencher. Specific examples thereof can include those shown below, but are not limited thereto.

[0341] [Chemical Formula 77]

[0342]

[0343] The aforementioned quencher can further include a polymer-type quencher described in Japanese Patent Application Publication No. 2008-239918. This improves the rectangularity of the resist after patterning by aligning to the surface of the resist film after coating of the resist composition. The polymer-type quencher also has the effect of preventing film loss and pattern rounding when a protective film for immersion exposure is used.

[0344] When the chemical amplification resist composition of the present application contains a quencher, the content thereof is preferably 0 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, relative to 80 parts by mass of the base polymer (e.g., (A) high molecular compound). The aforementioned quencher can be used alone or in combination with two or more kinds.

[0345] [(D) Fluorine-containing polymer]

[0346] The chemical amplification resist composition of the present application can also contain a fluorine-containing polymer containing a repeating unit represented by the following general formula (D1) (hereinafter also referred to as repeating unit D1), and at least one kind selected from the group consisting of repeating units represented by the following general formulae (D2), (D3), (D4), and (D5) (hereinafter also referred to as repeating units D2, D3, D4, and D5, respectively), in order to increase the contrast, prevent chemical flare of the acid at the time of irradiation with high-energy rays, and prevent intermixing of the acid from the antistatic film at the time of the process of coating the antistatic film material on the resist, and to suppress unintended and undesirable pattern degradation. The aforementioned fluorine-containing polymer also has a surface activity function, and thus can prevent reattachment of insolubles that can be generated during the development process to the substrate, and thus also exerts an effect of preventing development defects.

[0347] [Chemical 78]

[0348]

[0349] In the formula, R B are each independently a hydrogen atom or a methyl group. R C are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 41 is a hydrogen atom, or a linear or branched monovalent hydrocarbon group having 1 to 5 carbons, which can have a heteroatom inserted between carbon-carbon bonds. R 42 is a linear or branched monovalent hydrocarbon group having 1 to 5 carbons, which can have a heteroatom inserted between carbon-carbon bonds. R 43a , R 43b , R 45a , and R 45b are each independently a hydrogen atom, or a linear, branched, or cyclic alkyl group having 1 to 10 carbons. R 44 , R 46 , R 47 , and R 48Each of the following is independently a hydrogen atom, a linear, branched, or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, a fluorinated monovalent hydrocarbon group, or an acid-instable group, and R 44 R 46 R 47 and R 48 When the group is a monovalent hydrocarbon group or a fluorinated monovalent hydrocarbon group, an ether group or a carbonyl group may be inserted between the carbon-carbon bonds. x is an integer from 1 to 3. y is an integer satisfying 0 ≤ y ≤ 5 + 2z - x. z is 0 or 1. m is an integer from 1 to 3. X 1 It is a single bond, -C(=O)-O- or -C(=O)-NH-. X 2 It is a linear, branched, or cyclic hydrocarbon group or fluorinated hydrocarbon group with a carbon number of 1 to 20 and a valence of (m+1).

[0350] R 41 R 42 R 44 R 46 R 47 R 48 Examples of the aforementioned monovalent hydrocarbon groups include alkyl, alkenyl, and ynyl groups, with alkyl being preferable. Examples of the aforementioned alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and n-pentyl. Furthermore, heteroatoms such as oxygen, sulfur, and nitrogen atoms can be inserted between the carbon-carbon bonds of these groups.

[0351] In general formula (D1), -OR 41 It should preferably be a hydrophilic group. In this case, R... 41 Suitable for hydrogen atoms, alkyl groups with 1 to 5 carbon atoms with oxygen atoms inserted between carbon-carbon bonds, etc.

[0352] Repeating unit D1 can be listed as shown below, but is not limited to these. Additionally, in the following formula, R... B Same as above.

[0353] [Chemistry 79]

[0354]

[0355] [Chemistry 80]

[0356]

[0357] In repeating unit D1, X 1 It is preferable to use -C(=O)-O- or -C(=O)-NH-. Additionally, R B Methyl is preferable. X 1 The presence of a carbonyl group improves the ability to capture acids from the antistatic membrane. Also, R BWhen R1is a methyl group, a rigid polymer having a higher glass transition temperature (Tg) is obtained, and diffusion of the acid is inhibited. Thus, the temporal stability of the resist film is improved, and the resolution and pattern shape are not deteriorated.

[0358] In General Formulae (D2) and (D3), R 43a , R 43b , R 45a , and R 45b representable alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a cyclobutyl group, an n-pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an adamantyl group, norbornyl group, and the like. Among them, a linear, branched, or cyclic alkyl group having 1 to 6 carbons is preferable.

[0359] In General Formulae (D2) to (D5), R 44 , R 46 , R 47 , and R 48 representable monovalent hydrocarbon groups include an alkyl group, an alkenyl group, an alkynyl group, and the like, and an alkyl group is preferable. The aforementioned alkyl group can include, in addition to the aforementioned ones, an n-undecyl group, an n-dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and the like. Also, a fluorinated monovalent hydrocarbon group can include a group in which a part or all of hydrogen atoms bonded to a carbon atom of the aforementioned monovalent hydrocarbon group are replaced with fluorine atoms.

[0360] X 2 representable linear, branched, or cyclic (m+1)-valent hydrocarbon groups or fluorinated hydrocarbon groups having 1 to 20 carbons can include a group further removed m hydrogen atoms from the aforementioned monovalent hydrocarbon group or fluorinated monovalent hydrocarbon group.

[0361] Specific examples of the repeating units D2 to D5 can include the following ones, but are not limited thereto. In the following formulae, R C are the same as the aforementioned ones.

[0362] [Chem. 81]

[0363]

[0364] [Chem. 82]

[0365]

[0366] The content of the repeating unit D1 is preferably 5 to 85 mol%, and more preferably 15 to 80 mol% in the total repeating units of the (D) fluorine-containing polymer. The repeating units D2 to D5 can be used alone or in combination of two or more, and the content thereof is preferably 15 to 95 mol%, and more preferably 20 to 85 mol% in the total repeating units of the (D) fluorine-containing polymer.

[0367] The (D) fluorine-containing polymer can also contain other repeating units in addition to the aforementioned repeating units. Such repeating units can include those described in paragraphs

[0046] to

[0078] of Japanese Patent Application Publication No. 2014-177407, among others. When the (D) fluorine-containing polymer contains other repeating units, the content of the other repeating units is preferably 50 mol% or less, based on the total repeating units.

[0368] The (D) fluorine-containing polymer can be synthesized by copolymerizing each monomer after protecting the functional group as needed using a known method, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited and is preferably radical polymerization, anionic polymerization. For these methods, refer to Japanese Patent Application Publication No. 2004-115630.

[0369] The weight average molecular weight (Mw) of the (D) fluorine-containing polymer is preferably 2,000 to 50,000, more preferably 3,000 to 20,000. If the Mw is 2,000 or more, diffusion of the acid can be prevented, and resolution and stability over time can be sufficiently maintained. If the Mw is 50,000 or less, the solubility in a solvent is sufficiently high, and there are no cases where coating defects occur. Also, the molecular weight distribution (Mw / Mn) of the (D) fluorine-containing polymer is preferably 1.0 to 2.2, more preferably 1.0 to 1.7.

[0370] The content of the (D) fluorine-containing polymer is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 80 parts by mass of the base polymer (e.g., the (A) high molecular compound). In addition, the (D) fluorine-containing polymer is not limited to the above and can also be used as described in paragraphs

[0027] to

[0041] of Japanese Patent No. 4466881, for example.

[0371] [(E) Organic Solvent]

[0372] The chemically amplified resist composition of the present application can also contain an organic solvent as the (E) component. The aforementioned organic solvent is not particularly limited as long as it can dissolve each component contained in the composition.

[0373] Examples of such organic solvents include, for example, ketones such as cyclohexanone and methyl-2-pentyl ketone as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; lactones such as γ-butyrolactone; and mixtures thereof. When using acid-unstable groups of acetals, high-boiling-point alcohol solvents can be added to accelerate the deprotection reaction of the acetal. Specifically, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol, etc., can also be added.

[0374] Among these organic solvents, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, and mixtures thereof are preferred.

[0375] (E) The content of the organic solvent relative to 100 parts by mass of the base polymer (e.g., (A) polymer) is preferably 200 to 10,000 parts by mass, and more preferably 400 to 5,000 parts by mass. (E) One organic solvent may be used alone, or two or more may be used in combination.

[0376] [(F) Crosslinking agent]

[0377] When the chemically amplified resist composition of the present invention is a negative resist composition, and the aforementioned polymer compound of component (A) does not contain a repeating unit represented by general formula (A2), it is preferable to incorporate a crosslinking agent. On the other hand, when the aforementioned polymer compound of component (A) contains a repeating unit represented by general formula (A2), a crosslinking agent may not be incorporated.

[0378] Specific examples of crosslinking agents that can be used in this invention include melamine compounds, guanidine compounds, glycourea compounds, urea compounds, epoxy compounds, isocyanate compounds, azide compounds, and compounds containing double bonds such as alkenyl ether groups, which are substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups. These can be used as additives or introduced into polymer side chains as dangling groups. Furthermore, compounds containing hydroxyl groups can also be used as crosslinking agents.

[0379] Among the aforementioned crosslinking agents, epoxy compounds can include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, trihydroxyethyl ethane triepoxypropyl ether, and the like.

[0380] Melamine compounds can include compounds in which 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, hexamethoxymethyl melamine, hexahydroxymethyl melamine, or the like are methylated with methoxymethyl groups, or mixtures thereof, hexamethoxyethyl melamine, hexacyanoethyl melamine, hexacyanoethyl melamine, or the like.

[0381] Guanamine compounds can include compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl guanamine, tetramethoxymethyl guanamine, tetrahydroxymethyl guanamine, or the like are methylated with methoxymethyl groups, or mixtures thereof, tetramethoxyethyl guanamine, tetraacyloxy guanamine, tetrahydroxymethyl guanamine, or the like.

[0382] Glycoluril compounds can include tetrahydroxymethyl glycoluril, tetramethoxymethyl glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl glycoluril, or the like are methylated with methoxymethyl groups, or mixtures thereof, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl glycoluril, or the like are acyloxymethylated.

[0383] Urea compounds can include tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds in which 1 to 4 hydroxymethyl groups of tetrahydroxymethyl urea, or the like are methylated with methoxymethyl groups, or mixtures thereof, tetramethoxyethyl urea, and the like.

[0384] Isocyanate compounds can include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, and the like.

[0385] Azide compounds can include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylenebisazide, 4,4'-oxybisazide, and the like.

[0386] Alkenyl ether-containing compounds can include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentatetraol trivinyl ether, neopentatetraol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

[0387] The blending amount of the cross-linking agent is preferably 0.5 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to 80 parts by mass of the aforementioned high molecular compound of the component (A). If it is within the aforementioned range, the concern that the resolution will decrease due to the interconnection of the patterns is low. One kind of cross-linking agent can be used alone, or two or more kinds of cross-linking agents can be used in combination.

[0388] [(G) surfactant]

[0389] In the chemical amplification resist composition of the present application, a conventional surfactant can also be added in order to improve the coatability to the substrate to be processed. When a surfactant is used, there are many examples known as described in Japanese Patent Application Publication No. 2004-115630, and they can be selected by reference. The content of the surfactant is preferably 0 to 5 parts by mass, relative to 80 parts by mass of the aforementioned high molecular compound of the component (A), but when the component (D) is contained in the resist, the component (D) also functions as a surfactant, and therefore the surfactant can not be added in the resist.

[0390] In terms of the design of the positive resist composition, the dissolution rate of the resist coating film to the alkali developer is 10 nm / min or less, preferably 8 nm / min or less, more preferably 6 nm / min or less. When the coating film coated on the substrate falls within the thin film region (100 nm or less), the influence of the loss of the pattern film by the alkali development becomes large, and when the alkali dissolution rate of the positive resist composition is greater than 10 nm / min, the pattern collapses and a fine pattern cannot be formed. In particular, in the production of a photomask in which no defect is required, the tendency to have a strong development process is significant. In addition, in the present application, the dissolution rate to the alkali developer is a value calculated from the amount of film loss when the positive resist composition of the present application is spin-coated on a 6-inch silicon wafer, baked at 110°C for 240 seconds, and then developed with a 2.38% TMAH aqueous solution for 80 seconds.

[0391] In terms of the design of the negative resist composition, in advanced photolithography, the dissolution rate of the resist coating film to the alkali developer is 0.5 nm / sec or more, preferably 1 nm / sec or more, in view of the development residue after the alkali development. When the alkali dissolution rate of the negative resist composition is 0.5 nm / sec or more, the concern that a development residue is generated after the alkali development and a defect is caused is low. In the present application, the dissolution rate to the alkali developer is a value calculated from the amount of film loss when the negative resist composition of the present application is spin-coated on a 6-inch silicon wafer, baked at 110°C for 240 seconds, and then developed with a 2.38% TMAH aqueous solution for 60 seconds.

[0392] [Method for producing high molecular compound]

[0393] Further, the present application provides a method for producing a high molecular compound used in a chemically amplified resist composition, which is a method for producing a high molecular compound containing one or two or more repeating units, by polymerizing a polymerizable monomer of which the residual oligomer of two or more polymers is 1000 ppm or less.

[0394] At this time, at least one of the repeating units of the polymerizable monomer of which the residual oligomer of the two or more polymers is 1000 ppm or less is preferably the repeating unit A1 represented by the general formula (Al) or the repeating unit A2 represented by the general formula (A2).

[0395] If so, by using a material in which the oligomer component is suppressed at the stage of the monomer before polymerization, rather than at the stage of the polymer, a high molecular compound used in a chemically amplified resist composition which satisfies good resolution, pattern shape, line edge roughness, and which can suppress a development residue defect which is a cause of a mask defect can be produced.

[0396] [Method for forming a resist pattern]

[0397] Further, the present application provides a method for forming a resist pattern, comprising:

[0398] (1) a step of forming a resist film on a substrate using the above-mentioned chemically amplified resist composition,

[0399] (2) a step of irradiating a pattern to the above-mentioned resist film using a high energy ray, and

[0400] (3) a step of developing the above-mentioned resist film on which the pattern has been irradiated using an alkali developer.

[0401] The above-mentioned substrate can be, for example, a substrate for integrated circuit production (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, an organic antireflection film, etc.), or a substrate for mask circuit production (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, SiON, SiONC, CoTa, NiTa, TaBN, SnO2, etc.). The chemically amplified resist composition of the present application is applied to the above-mentioned substrate by a method such as spin coating so that the film thickness becomes, for example, 0.03 to 2 μm, and is prebaked on a hot plate, preferably at 60 to 150°C for 1 to 20 minutes, more preferably at 80 to 140°C for 1 to 10 minutes, to form a resist film.

[0402] Then, the aforementioned resist film is exposed to high energy rays, and a pattern is irradiated. The aforementioned high energy rays can be exemplified by ultraviolet rays, far ultraviolet rays, excimer laser (KrF, ArF, etc.), EUV (extreme ultraviolet rays), X-rays, γ-rays, synchrotron radiation, EB, etc. In the present application, it is desirable to perform exposure using EUV or EB (electron beam).

[0403] When ultraviolet rays, far ultraviolet rays, excimer laser, EUV, X-rays, γ-rays, or synchrotron radiation is used as the aforementioned high energy rays, it is desirable that the exposure dose using a mask for forming the intended pattern becomes 1 to 500 mJ / cm 2 and becomes 10 to 400 mJ / cm 2 It is more desirable to perform irradiation in this way. When EB is used, in order to form the intended pattern, it is desirable that the exposure dose directly becomes 1 to 500 μC / cm 2 and becomes 10 to 400 μC / cm 2 It is more desirable to perform irradiation in this way.

[0404] The exposure can use a general exposure method, and in addition thereto, a method of immersing a mask and a resist can be used as occasion demands. At this time, a protective film which is not soluble in water can also be used.

[0405] Then, post-exposure baking (PEB) is performed on a hot plate for 1 to 20 minutes at a temperature of 60 to 150°C, and more desirably for 1 to 10 minutes at a temperature of 80 to 140°C.

[0406] Thereafter, by using a developer of an aqueous alkali solution of 0.1 to 5 mass%, and desirably 2 to 3 mass% of TMAH, etc., a pattern of the intended pattern is formed on a substrate by a general method of a dip method, a puddle method, a spray method, etc. for 0.1 to 3 minutes, and more desirably for 0.5 to 2 minutes.

[0407] Further, the topmost surface of the aforementioned substrate is desirably composed of a material containing at least one of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

[0408] In addition, the chemically amplified resist composition of the present application is particularly useful in that it can suppress development defects which can become mask defects. Further, the chemically amplified resist composition of the present application can effectively reduce development defects even if adhesiveness differs depending on the type of substrate. Such a substrate can be exemplified by a substrate in which a metal chromium or a chromium compound containing one or more light elements selected from oxygen, nitrogen, and carbon is sputter-deposited on the topmost surface, a substrate in which SiO, SiO xa substrate of a tantalum compound, a molybdenum compound, a cobalt compound, a nickel compound, a tungsten compound, a tin compound, and the like. The chemically amplified resist composition of the present application is particularly useful for pattern formation using a blank photomask as a substrate. At this time, the blank photomask can be either a transmissive type or a reflective type.

[0409] If it is the method for forming a resist pattern of the present application, even when a substrate (for example, a blank photomask) in which the material of the most surface is composed of a material that easily causes an influence on the shape of the resist pattern, such as a material containing chromium or silicon or tantalum, is used, a pattern of high resolution in which the influence of development defects is suppressed can be obtained.

[0410] [Blank photomask]

[0411] Thus, the present application provides a blank photomask coated with the above-mentioned chemically amplified resist composition. The chemically amplified resist composition of the present application is particularly useful for pattern formation using a blank photomask as a substrate.

[0412] [Examples]

[0413] Hereinafter, the present application will be specifically described by way of synthesis examples, examples, and comparative examples, but the present application is not limited by these descriptions. In the following examples, Me represents a methyl group. Also, the copolymerization composition ratio is a molar ratio, and the weight average molecular weight (Mw) represents a polystyrene-converted weight average molecular weight measured by gel permeation chromatography (GPC). Also, the value of the oligomer is a calculated value of the concentration converted from each monomer, measured by LC-MS (device name: Thermo Fisher SCIENTIFIC / Vanquish (LC system), Q-Exactive (MS)).

[0414] [1] Synthesis of monomers

[0415] [Synthesis Example 1] Synthesis of monomer (1), monomer (2)

[0416] In a 3L 4-necked flask under nitrogen, 42.1 g of magnesium and 50 mL of THF were placed, and a solution of 200 g of 4-chlorostyrene dissolved in 200 mL of THF was added dropwise over 1 hour at room temperature, and after warming to 80°C, stirring was performed for 3 hours to prepare Grignard reagent. The obtained Grignard reagent was cooled in an ice bath, and a solution of 100.6 g of acetone dissolved in 200 mL of THF was added dropwise over 1 hour. After stirring overnight, a 15 mass% aqueous ammonium chloride solution (1,000 g) was added dropwise to stop the reaction. A usual aqueous work-up was performed. Thereafter, 0.02 g of 4-tert-butylcatechol was added to the crude product, and purification was performed by distillation under reduced pressure at a bath temperature of 90°C and 20 Pa to obtain the objective monomer (1) of the following structure, 145.2 g (yield 62%). The 2-6 polymer oligomer was 1700 ppm.

[0417] [Chemical Formula 83]

[0418]

[0419] After the aqueous work-up, 0.2 g of 4-tert-butylcatechol was added, and purification was performed by distillation under reduced pressure at a bath temperature of 70°C and 5 Pa, and otherwise, the objective monomer (2) was obtained in the same formulation as that of the synthesis of the above monomer (1), 140.5 g (yield 60%). The 2-6 polymer oligomer was 90 ppm.

[0420] [Synthesis Example 2] Synthesis of Monomer (3), Monomer (4)

[0421] In a 3L 4-necked flask under nitrogen, 27.8 g of magnesium and 50 mL of THF were placed, and a solution of 200 g of l-chloro-4-[(l-methylcyclopentyl)oxy]benzene dissolved in 200 mL of THF was added dropwise over 1 hour at room temperature, and after warming to 80°C, stirring was performed for 3 hours to prepare Grignard reagent. The obtained Grignard reagent was cooled in an ice bath, and 2.5 g of dichloro(l,3-bis(diphenylphosphino)propane)nickel was added to stand for 30 minutes, and a solution of 151.2 g of bromovinyl dissolved in 200 mL of THF was added dropwise over 1 hour. After stirring overnight, a 15 mass% aqueous ammonium chloride solution (1,000 g) was added dropwise to stop the reaction. A usual aqueous work-up was performed. Thereafter, 0.02 g of 4-tert-butylcatechol was added to the crude product, and purification was performed by distillation under reduced pressure at a bath temperature of 100°C and 20 Pa to obtain the objective monomer (3) of the following structure, 111.3 g (yield 58%). The 2-6 polymer oligomer was 1600 ppm.

[0422] [Chemical Formula 84]

[0423]

[0424] After the aqueous work-up, 0.2 g of 4-tert-butylcatechol was added, and purification was performed by reduced pressure distillation at a bath temperature of 80°C and 5 Pa. Other than this, the target monomer (4) 105.6 g (yield 55%) was obtained in the same formulation as the synthesis formulation of the above monomer (3). The 2-6 polymer oligomer was 110 ppm.

[0425] [Synthesis Example 3] Synthesis of monomer (5), monomer (6)

[0426] 200 g of 4-acetyloxyphenylstyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 800 g of ethyl acetate, and a solution in which 73.5 g of sodium methoxide had been dissolved in 200 mL of methanol was added dropwise thereto over 1 hour under ice cooling. After stirring for 3 hours thereafter, the reaction was stopped by adding 800 g of water. The usual aqueous work-up was performed. Thereafter, 0.02 g of 4-tert-butylcatechol was added to the crude product, and concentration was performed at a bath temperature of 50°C to obtain the target monomer (5) of the following structure 121.5 g (yield 82%). The 2-6 polymer oligomer was 1650 ppm.

[0427] [Chem. 85]

[0428]

[0429] After the aqueous work-up, 0.2 g of 4-tert-butylcatechol was added, and concentration was performed at a bath temperature of 35°C. Other than this, the target monomer (6) 118.5 g (yield 80%) was obtained in the same formulation as the synthesis formulation of the above monomer (5). The 2-6 polymer oligomer was 160 ppm.

[0430] [Synthesis Example 4] Synthesis of monomer (7), monomer (8)

[0431] To 49.0 g (0.1 mole) of 1,1,3,3,3-pentafluoro-2-hydroxypropane-1-sulfonic acid triphenylsulfonium, 200 g of dichloromethane was added, 10.1 g (0.10 mole) of triethylamine and 2.4 g (0.2 mole) of N,N-dimethylaminopyridine were added, and stirring was performed under ice cooling. 10.0 g (0.10 mole) of methacrylic anhydride was added dropwise at a temperature of not more than 10°C. Further aging was performed for 15 minutes, dilute hydrochloric acid was added, and liquid separation was performed, and the organic layer was washed with 200 g of water three times, and the organic layer was concentrated, and diethyl ether was added to the residue to crystallize. The crystals were filtered, purified by silica gel column chromatography (eluent: dichloromethane-methanol mixed solvent), and recrystallized again using diethyl ether, and filtration and drying were performed, whereby the monomer (7) of the following structure was obtained (yield 51%). The 2-6 polymer oligomer was 1540 ppm.

[0432] [Chem. 86]

[0433]

[0434] 15 g of the monomer (7) synthesized in the above-described manner was dissolved in 30 g of methanol, and crystallization was performed by dropwise addition to 600 g of water, and filtration and drying were performed, whereby 12.3 g of the objective monomer (8) was obtained. The 2-6 polymer oligomer was 130 ppm.

[0435] [Synthesis Example 5] Synthesis of monomer (9), monomer (10)

[0436] 4-Chlorostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.) of the following structure was used (monomer (9)). The 2-6 polymer oligomer was 1800 ppm.

[0437] [Chem. 87]

[0438]

[0439] To 100 g of the monomer (9), 0.1 g of 4-tert-butylcatechol was added, and purification was performed by reduced pressure distillation at a bath temperature of 50°C and a pressure of 5 Pa, and 95.0 g of the objective monomer (10) was obtained. The 2-6 polymer oligomer was 280 ppm.

[0440] [Polymer Synthesis Example 1] Synthesis of Polymer 3

[0441] Under a nitrogen atmosphere, a solution of 49.3 g of 4-acetyloxy-styrene, 7.1 g of acenaphthylene, 23.6 g of monomer (4), 8.6 g of dimethyl-2,2'-azobis-(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V601), and 124 g of methyl ethyl ketone as a solvent was prepared in a 300 mL dropping funnel column. To another 500 mL polymerization flask, which was adjusted to a nitrogen atmosphere, 62 g of methyl ethyl ketone was added, and the above-prepared solution was added dropwise over 4 hours while being warmed to 80°C. After the completion of the dropwise addition, the polymerization temperature was maintained at 80°C while stirring was continued for 18 hours, and then the temperature was allowed to cool to room temperature. The resulting polymerization solution was added dropwise to 1300 g of hexane, and the copolymer that precipitated was separated by filtration. The filtered copolymer was washed twice with 500 g of hexane. The resulting copolymer was dissolved in a mixed solvent of 144 g of tetrahydrofuran and 48 g of methanol in a 1 L flask under a nitrogen atmosphere, and 22.3 g of ethanolamine was added, and stirring was performed at 60°C for 3 hours. The reaction solution was concentrated under reduced pressure, and the resulting concentrate was dissolved in a mixed solvent of 240 g of ethyl acetate and 60 g of water, and the resulting solution was transferred to a separatory funnel, and 11.1 g of acetic acid was added, and liquid-liquid separation was performed. The lower layer was removed, and 60 g of water and 14.8 g of pyridine were added to the resulting organic layer, and liquid-liquid separation was performed. The lower layer was removed, and 60 g of water was further added to the resulting organic layer to perform water washing and liquid-liquid separation (water washing and liquid-liquid separation was performed a total of 5 times). The organic layer after the liquid-liquid separation was concentrated, and dissolved in 130 g of acetone, and the resulting acetone solution was added dropwise to 1200 g of water, and the resulting crystallization precipitate was filtered, washed with water, and suction-filtered for 2 hours, and the resulting filtrate was again dissolved in 130 g of acetone, and the resulting acetone solution was added dropwise to 1200 g of water, and the resulting crystallization precipitate was filtered, washed with water, and dried to obtain 51.0 g of a white polymer. The resulting polymer was analyzed by 13 C-NMR, 1 H-NMR, and GPC, and the following analysis results were obtained.

[0442] [Chemical 88]

[0443]

[0444] [Polymer Synthesis Example 2] Synthesis of Polymer 22

[0445] Under a nitrogen atmosphere, 890 g of a 50.0 mass% propylene glycol monomethyl ether acetate (PGMEA) solution of 4-hydroxystyrene, 47.7 g of acenaphthylene, 310 g of a 54.7 mass% PGMEA solution of monomer (2), 87.0 g of 1,1,3,3,3-pentafluoro-2-methylacryloyloxypropane-1-sulfonic acid triphenylsulfonium, 96.1 g of dimethyl-2,2'-azobis-(2-methylpropionate) (and OUCHI SHU KAGAKU K.K. manufactured V-601), and 360 g of γ-butyrolactone and 220 g of PGMEA as a solvent were added to a 3,000 mL dropping funnel column, and a solution was prepared. To another 5,000 mL polymerization flask adjusted to a nitrogen atmosphere, 580 g of γ-butyrolactone was added, and the above prepared solution was added dropwise over 4 hours while being warmed to 80°C. After the dropwise addition was completed, the polymerization temperature was maintained at 80°C while stirring was continued for 18 hours, and then it was cooled to room temperature. The resulting polymerization solution was added dropwise to 22.5 kg of diisopropyl ether, and the copolymer was precipitated. The diisopropyl ether was removed by decantation, and the copolymer was dissolved in 2,250 g of acetone. This acetone solution was added dropwise to 22.5 kg of diisopropyl ether, and the copolymer was precipitated by filtration. The filtered copolymer was again dissolved in 2,250 g of acetone, and this acetone solution was added dropwise to 22.5 kg of water, and the copolymer was precipitated by filtration. Thereafter, it was dried at 40°C for 40 hours, and 700 g of a polymer 22 was obtained as a white polymer. The obtained polymer was measured by 13 C-NMR, 1 H-NMR and GPC, and the following analysis results were obtained.

[0446] [Chemical Formula 89]

[0447]

[0448] [Polymer Synthesis Example 3] Synthesis of Polymers 1 to 2, 4 to 21, 23 to 32, and Comparative Polymers 1 to 5

[0449] The polymers 1 to 2, 4 to 21, 23 to 32, comparative polymers 1 to 5 were synthesized by the same procedure as in the polymer synthesis example 1 or 2 except that the kind of each polymerizable monomer and the introduction ratio (molar ratio) were changed. The kinds of monomers and the introduction ratios of the polymers 1 to 32 and the comparative polymers 1 to 5 are shown in Tables 1-1 to 1-3. Also, the structure of the polymerizable monomer of the repeating unit introduced into the polymer is shown in Tables 2 to 6. In addition, the Mw of the polymer was measured as a polystyrene conversion value by GPC using tetrahydrofuran as a solvent. However, in the case of the polymers containing P-1 to P-6, the Mw was measured as a polystyrene conversion value by GPC using dimethylformamide as a solvent. The Mw of the polymers 1 to 32 and the comparative polymers 1 to 5 was between 2500 and 21000, and the Mw / Mn was between 1.4 and 2.2.

[0450] [Table 1-1]

[0451]

[0452] [Table 1-2]

[0453]

[0454] [Table 1-3]

[0455]

[0456] [Table 2]

[0457]

[0458] In the case of the polymerizable monomers used to obtain A-1, the above-described monomers (5), (6) were used.

[0459] [Table 3]

[0460]

[0461] In the case of the polymerizable monomers used to obtain B-3, the above-described monomers (9), (10) were used.

[0462] [Table 4]

[0463]

[0464] In the case of the polymerizable monomers used to obtain C-1, the above-described monomers (3), (4) were used.

[0465] [Table 5]

[0466]

[0467] In the case of the polymerizable monomers used to obtain E-1, the above-described monomers (1), (2) were used.

[0468] [Table 6]

[0469]

[0470] As the polymerizable monomer to obtain P-1, the above-described monomers (7), (8) were used.

[0471] Preparation of resist compositions

[0472] [Examples 1-1 to 1-41, Comparative Examples 1-1 to 1-5]

[0473] The polymer (polymers 1 to 32, comparative polymers 1 to 5) synthesized in the synthesis examples, the acid generator (PAG-A to PAG-F), and the acid diffusion controller (Q-1 to Q-4) were dissolved in an organic solvent in the composition shown in Table 7, and the resulting solutions were filtered using a 10 nm size nylon filter and a 3 nm UPE filter, whereby resist compositions (R-1 to R-41, CR-1 to CR-5) were respectively prepared.

[0474] As the organic solvent of the resist compositions prepared in Examples 1-1 to 1-41 and Comparative Examples 1-1 to 1-5 in Tables 7-1 to 7-3, a mixed solvent of 1,204 parts by mass of PGMEA, 1,204 parts by mass of ethyl lactate (EL), and 1,606 parts by mass of propylene glycol monomethyl ether (PGME) was used. Also, in some of the compositions, a fluorine-containing polymer (D) (polymers D1 to D2) was added as an additive; tetramethoxymethyl glycoluril (TMGU) was added as a crosslinking agent. Also, in some of the compositions, PF-636 (manufactured by OMNOVA SOLUTIONS) was added as a surfactant.

[0475] In addition, the structures of Q-1 to 4, PAG-A to PAG-F, and polymers D1 to D2 are described below.

[0476] [Chem. 90]

[0477]

[0478] [Chem. 91]

[0479]

[0480] [Chem. 92]

[0481]

[0482] [Table 7-1]

[0483]

[0484] [Table 7-2]

[0485]

[0486] [Table 7-3]

[0487]

[0488] [Resist residue evaluation]

[0489] The resist compositions (R-1 to R-41, CR-1 to CR-5) prepared were spin-coated on a 152 mm square blank mask whose top surface was a silicon oxide film, which had been subjected to hexamethyldisilazane (HMDS) vapor prime treatment, using an ACT-M (Tokyo Ohka Kogyo Co., Ltd.) at 110°C for 600 seconds to give a resist film having a thickness of 80 nm. The thickness of the resist film obtained was measured using an optical thickness meter, NANOSPEC (Nanometrics, Inc.). The measurement was performed at 81 points in the plane of the blank mask excluding the outer edge portion from the outer edge of the blank mask to the inner side of 10 mm, and the average value and the range of the thickness were calculated.

[0490] The resist compositions (R-16 to R-41, CR-3 to CR-5) were subjected to baking at 120°C for 600 seconds without drawing and after development with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, evaluation of the resist residue was performed using a mask defect inspection device (M9650, Lasertec Co., Ltd.). Also, for the resist compositions (R-1 to R-15, CR-1 to CR-2), drawing was performed using an electron beam exposure device (EBM-5000plus, NuFlare Technology, Inc., accelerating voltage 50 keV), PEB was performed at 120°C for 600 seconds, and after development with a 2.38 mass% aqueous solution of TMAH, evaluation of the resist residue was performed using a mask defect inspection device (M9650, Lasertec Co., Ltd.). The total number of defects after development is shown in Table 8.

[0491] [Table 8]

[0492]

[0493]

[0494] As is clear from the results in Table 8, the chemically amplified resist composition of the present application containing a polymer polymerized from a polymerizable monomer having reduced residual oligomer can greatly reduce the number of defects caused by resist residue, compared with known resist compositions.

[0495] Further, the above-mentioned resist compositions (R-1 to R-41, CR-1 to CR-5) were spin-coated on a 152 mm square blank mask whose top surface was a silicon oxide film, which had been subjected to hexamethyldisilazane (HMDS) vapor prime treatment, using ACT-M (Tokyo Ohka Kogyo Co., Ltd.) and prebaked at 110°C for 600 seconds on a hot plate, to form a resist film having a thickness of 80 nm. The resist film was then exposed using an electron beam exposure device (NuFlare Technology, Inc. EBM-5000plus, accelerating voltage 50 kV), subjected to PEB at 110°C for 600 seconds, and developed using a 2.38 mass% TMAH aqueous solution, to obtain a negative and positive pattern.

[0496] The obtained resist pattern was evaluated as follows. The obtained blank mask provided with a pattern was observed with an SEM (scanning electron microscope) to determine the optimum exposure dose (μC / cm2) for a 1:1 line and space (LS) of 200 nm, and the minimum size for a 1:1 line and space (LS) of 200 nm was determined as the resolution (limiting resolution) when the exposure dose was 1:1. Any of the resist compositions could achieve high resolution performance of 60 nm or less for a 1:1 line and space (LS). 2

[0497] If the chemically amplified resist composition of the present application is used, post-development residue that can become a defect in a mask can be suppressed. Further, the resist pattern forming method using the chemically amplified resist composition is useful for optical lithography in the manufacture of semiconductor elements, particularly in the processing of a blank photomask.

[0498] Further, the present application is not limited to the above-described embodiments. The above-described embodiments are illustrative, and those having substantially the same configuration as that described in the technical idea of the claims of the present application and exerting the same effects are included in the technical scope of the present application.​

Claims

1. A chemically amplified resist composition, wherein the chemically amplified resist composition is a chemically amplified negative resist composition, characterized in that it contains: (A) A polymeric compound, wherein component (A) is a polymeric compound containing a repeating unit A2 represented by the following general formula (A2), and the repeating unit A2 is a repeating unit polymerized from polymeric monomers in which the residual oligomer of 2 to 6 polymers is less than 1000 ppm. In the formula, R A It consists of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; A 1 It is a single bond, or a saturated hydrocarbon group with 1 to 10 carbon atoms, and the -CH2- constituting the saturated hydrocarbon group can also be replaced by -O-; R 1 Each of the following can be independently a halogen atom, a 2-8 carbonyl carbonyl group that can be substituted by a halogen atom, a 1-6 carbonyl group that can be substituted by a halogen atom, or a 1-6 carbonyl carbonyl group that can be substituted by a halogen atom; W 1 Rx is a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group that may also have substituents, and the -CH2- constituting the aliphatic hydrocarbon group may also be replaced by -O-, -C(=O)-, -OC(=O)- or -C(=O)-O-; Rx and Ry are independently hydrogen atoms, or saturated hydrocarbon groups having 1 to 15 carbon atoms that may be replaced by hydroxyl or saturated hydrocarbon oxygen groups, or aryl groups that may also have substituents; however, Rx and Ry will not both be hydrogen atoms at the same time; furthermore, Rx and Ry may also bond to each other and form a ring together with the carbon atoms they are bonded to; y is an integer from 0 to 2; u is 0 or 1; f is an integer that satisfies 0≤f≤5+2y-g; g is an integer from 1 to 3.

2. The chemically amplified resist composition according to claim 1, wherein, The component (A) is a polymeric compound containing a repeating unit A3 represented by the following general formula (A3); In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 11 Each of the following can be independently a halogen atom, a 2-8 carbonyl carbonyl group that can be substituted by a halogen atom, a 1-6 carbonyl group that can be substituted by a halogen atom, or a 1-6 carbonyl carbonyl group that can be substituted by a halogen atom; A 1 It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and the -CH2- constituting the saturated alkylene group can also be replaced by -O-; s is 0 or 1; w is an integer from 0 to 2; a is an integer satisfying 0≤a≤5+2w-b; b is an integer from 1 to 3.

3. The chemically amplified resist composition according to claim 1 or 2, wherein, The component (A) is a polymeric compound containing at least one repeating unit A4 to A11 represented by the following general formulas (A4) to (A11); In the formula, R B Each can be independently a hydrogen atom or a methyl group; Z 1 It is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or -OZ. 11 -、-C(=O)-OZ 11 -or-C(=O)-NH-Z 11 -, Z 11 It is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a phenylene, naphthylene, or a combination thereof having 7 to 18 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 2 For single key or -Z 21 -C(=O)-O-,Z 21 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 3 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, -OZ 31 -、-C(=O)-OZ 31 -or-C(=O)-NH-Z 31 -, Z 31 It is an aliphatic hydrocarbon group, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, or a combination thereof with 7 to 20 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 4 It is a single bond or may contain a hydrocarbon group with 1 to 30 carbon atoms; k 1 and k 2 Each can be independently 0 or 1, but Z 4 When it is a single bond, k 1 and k 2 It is 0; R 21 ~R 38 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; also, R 21 and R 22 They can also bond to each other and form rings together with the sulfur atoms they are bonded to, and R 23 and R 24 R 26 and R 27 or R 29 and R 30 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; R HF It is a hydrogen atom or a trifluoromethyl group; Xa - It is a non-nucleophilic relative ion.

4. The chemically amplified resist composition according to claim 1 or 2, wherein, The component (A) is a polymeric compound containing at least one repeating unit A12 to A14 represented by the following general formulas (A12), (A13) and (A14); In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 13 and R 14 Each of the following is independently a hydroxyl group, a halogen atom, an acetoxy group, a linear or branched or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen, a linear or branched or cyclic alkyl group having 1 to 8 carbon atoms that may be substituted with a halogen, a linear or branched or cyclic alkoxy group having 1 to 8 carbon atoms that may be substituted with a halogen, or a linear or branched or cyclic alkyl carbonyloxy group having 2 to 8 carbon atoms that may be substituted with a halogen; R 15 Acetyl, acetoxy, linear or branched or cyclic alkyl group having 1 to 20 carbon atoms, linear or branched or cyclic alkoxy group having 1 to 20 carbon atoms, linear or branched or cyclic acyloxy group having 2 to 20 carbon atoms, linear or branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, alkylthioalkyl group having 2 to 20 carbon atoms, halogen atom, nitro, cyano, sulfinyl, or sulfonyl group; A 3 It is a single bond, or a straight chain, or a branched or cyclic alkylene group having 1 to 10 carbon atoms, and may also have an ether bond inserted between carbon-carbon bonds; o and p are each an independent integer from 0 to 4; h is an integer of 0 or 1; j is an integer from 0 to 5; k is an integer from 0 to 2.

5. The chemically amplified resist composition according to claim 1, wherein, The component (A) is a polymeric compound containing repeating unit A2 represented by the general formula (A2) and repeating unit A3 represented by the general formula (A3) below, but not containing repeating units A4 to A11 represented by the general formulas (A4) to (A11) below. In the formula, R A It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R 11 Each of the following can be independently a halogen atom, a 2-8 carbonyl carbonyl group that can be substituted by a halogen atom, a 1-6 carbonyl group that can be substituted by a halogen atom, or a 1-6 carbonyl carbonyl group that can be substituted by a halogen atom; A 1 It is a single bond or a saturated alkylene group with 1 to 10 carbon atoms, and the -CH2- constituting the saturated alkylene group can also be replaced by -O-; s is 0 or 1; w is an integer from 0 to 2; a is an integer satisfying 0≤a≤5+2w-b; b is an integer from 1 to 3; In the formula, R B Each can be independently a hydrogen atom or a methyl group; Z 1 It is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining them, or -OZ. 11 -、-C(=O)-OZ 11 -or-C(=O)-NH-Z 11 -, Z 11 It is an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a phenylene, naphthylene, or a combination thereof having 7 to 18 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 2 For single key or -Z 21 -C(=O)-O-,Z 21 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; Z 3 Single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, -OZ 31 -、-C(=O)-OZ 31 -or-C(=O)-NH-Z 31 -, Z 31 It is an aliphatic hydrocarbon group, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, or a combination thereof with 7 to 20 carbon atoms, and may also contain a carbonyl group, ester bond, ether bond, or hydroxyl group; Z 4 It is a single bond or may contain a hydrocarbon group with 1 to 30 carbon atoms; k 1 and k 2 Each can be independently 0 or 1, but Z 4 When it is a single bond, k 1 and k 2 It is 0; R 21 ~R 38 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; also, R 21 and R 22 They can also bond to each other and form rings together with the sulfur atoms they are bonded to, and R 23 and R 24 R 26 and R 27 or R 29 and R 30 They can also bond to each other and form rings together with the sulfur atoms they are bonded to; R HF It is a hydrogen atom or a trifluoromethyl group; Xa - It is a non-nucleophilic relative ion.

6. The chemically amplified resist composition according to claim 1, wherein, The (A) component is a polymeric compound containing either or both of the repeating units represented by the following general formula (A2-1) and the repeating units represented by the following general formula (A2-2), and also containing the repeating units represented by the following general formula (A3-1) and the repeating units represented by the following general formula (A5-1). In the formula, R A Rx and Ry are hydrogen atoms, fluorine atoms, methyl groups, or trifluoromethyl groups; Rx and Ry are independently hydrogen atoms, or 1 to 15 carbon saturated hydrocarbon groups that may be substituted with hydroxyl or saturated hydrocarbon oxygen groups, or aryl groups that may have substituents; however, Rx and Ry cannot both be hydrogen atoms simultaneously; furthermore, Rx and Ry can also bond to each other and form a ring together with the carbon atoms they are bonded to; g is an integer from 1 to 3; b is an integer from 1 to 3; R B Each can be independently a hydrogen atom or a methyl group; Z 2 For single key or -Z 21 -C(=O)-O-,Z 21 It may also contain a hydrocarbon group with 1 to 20 carbon atoms; R 23 ~R 25 Each can be independently a hydrocarbon group with 1 to 20 carbon atoms, which may also contain heteroatoms; also, R 23 and R 24 They can also bond to each other and form rings together with the sulfur atoms they are bonded to.

7. The chemically amplified resist composition according to claim 1, 5, or 6, wherein, The polymer of component (A) is a polymer of two or more polymerizable monomers, and the total residual oligomers of 2 to 6 polymers contained in all of the polymerizable monomers are less than 5000 ppm.

8. The chemically amplified resist composition according to claim 1, 5 or 6 further contains (B) an acid generating agent.

9. A blank photomask, characterized by being coated with a chemically amplified resist composition according to any one of claims 1 to 8.

10. A method for forming a resist pattern, characterized by comprising: (1) The step of forming a resist film on a substrate using the chemically amplified resist composition according to any one of claims 1 to 8. (2) The step of irradiating the resist film with high-energy rays to form a pattern, and (3) The step of developing the resist film with the irradiated pattern using an alkaline developer.

11. The method for forming a resist pattern according to claim 10, wherein, The high-energy rays are ArF excimer lasers, KrF excimer lasers, extreme ultraviolet light, or electron beams.

12. The method for forming a resist pattern according to claim 10 or 11, wherein, The outermost surface of the substrate is made of a material containing at least one of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

13. A method for manufacturing a polymer compound, which is a method for manufacturing the polymer compound used in the chemically amplified resist composition according to claim 1, characterized in that: The polymer compound is obtained by polymerizing at least one type of 2-6 polymer with a residual oligomer content of 1000 ppm or less, and at least one repeating unit obtained from the repeating unit of the repeating monomer with a residual oligomer content of 1000 ppm or less is a repeating unit A2 represented by the following general formula (A2). In the formula, R A It consists of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; A 1 It is a single bond, or a saturated hydrocarbon group with 1 to 10 carbon atoms, and the -CH2- constituting the saturated hydrocarbon group can also be replaced by -O-; R 1 Each of the following can be independently a halogen atom, a 2-8 carbonyl carbonyl group that can be substituted by a halogen atom, a 1-6 carbonyl group that can be substituted by a halogen atom, or a 1-6 carbonyl carbonyl group that can be substituted by a halogen atom; W 1 Rx is a hydrogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an aryl group that may also have substituents, and the -CH2- constituting the aliphatic hydrocarbon group may also be replaced by -O-, -C(=O)-, -OC(=O)- or -C(=O)-O-; Rx and Ry are independently hydrogen atoms, or saturated hydrocarbon groups having 1 to 15 carbon atoms that may be replaced by hydroxyl or saturated hydrocarbon oxygen groups, or aryl groups that may also have substituents; however, Rx and Ry will not both be hydrogen atoms at the same time; furthermore, Rx and Ry may also bond to each other and form a ring together with the carbon atoms they are bonded to; y is an integer from 0 to 2; u is 0 or 1; f is an integer that satisfies 0≤f≤5+2y-g; g is an integer from 1 to 3.

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