Chemically amplified positive resist composition and resist pattern forming method

Abstract

The invention relates to a chemically amplified positive resist composition and a resist pattern forming method. The present invention addresses the problem of providing: a chemically amplified positive resist composition capable of forming a resist film having extremely high resolution, low LER, excellent rectangularity, and suppressed influence of development load and development residue defects; and a method for forming a resist pattern using the chemically amplified positive resist composition. The solution of the present invention is a chemically amplified positive resist composition comprising: (A) a photoacid generator which is represented by formula (A) and which generates an acid due to the action of a high-energy ray; and (B) a base polymer that contains a polymer that has increased solubility in aqueous alkali due to the action of an acid and that contains a repeating unit represented by formula (B1). # imgabs0 #

Description

Technical Field

[0001] The invention relates to a chemically amplified positive resist composition and a resist pattern forming method. Background Art

[0002] In recent years, with the high integration of integrated circuits, more fine pattern formation is required. In the processing of patterns below 0.2μm, chemically amplified resist compositions using acid as a catalyst are mainly used. In addition, as the exposure source at this time, high-energy rays such as ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (EUV), and electron beams (EB) are used. In particular, EB lithography, which is used as an ultra-fine processing technology, is also indispensable for the processing method of blank photomasks when making photomasks for semiconductor manufacturing.

[0003] In EB lithography, the drawing by EB is generally performed without using a mask. In the case of positive type, a method of sequentially irradiating a fine area of ​​EB to the portion other than the area where the resist film is to remain is adopted; in the case of negative type, a method of sequentially irradiating a fine area of ​​EB to the area where the resist film is to remain is adopted. That is, because it is necessary to scan the entire finely divided area of ​​the processing surface, it takes more time than a one-time exposure using a photomask, and in order not to reduce the production volume, a high-sensitivity resist film is required. In particular, in the processing of blank photomasks, which are important uses, there are surface materials such as chromium compound films headed by chromium oxide formed on the photomask substrate, which can easily affect the pattern shape of the chemically amplified resist film. In order to maintain high resolution and the shape after etching, it is not dependent on the type of substrate, and keeping the pattern outline of the resist film as a rectangle is also considered to be one of the important properties. In addition, a small line edge roughness (LER) is also considered to be one of the important properties. In recent years, in order to achieve miniaturization, there is also the use of a multi-beam mask writing (MBMW) writing process in the processing of blank masks. At this time, a low-sensitivity resist (high-dose area) that is beneficial to roughness is used as the resist, and the optimization of the resist composition in this high-dose area has also received attention.

[0004] Regarding the control of sensitivity and pattern profile, various improvements have been made based on the selection, combination, process conditions, etc. of the materials used in the resist composition. One of the improvements is the suppression of the diffusion of acid, which has a significant impact on the resolution of the resist film. In the processing of photomasks, it is required that the shape of the resist pattern obtained does not change depending on the time from exposure to heating. A large part of the time-dependent change in the shape of the resist pattern is due to the diffusion of acid generated by exposure. This acid diffusion problem is not limited to photomask processing, but also has a great impact on sensitivity and resolution in general resist compositions, so a lot of research has been conducted.

[0005] Patent Documents 1 and 2 describe examples of reducing LER by increasing the barrier of acid generated from an acid generator to suppress acid diffusion. However, in such acid generators, the suppression of acid diffusion is still insufficient, so it is important to develop an acid generator with a smaller acid diffusion.

[0006] Patent Document 3 describes an example of controlling acid diffusion by introducing a repeating unit having a sulfonium structure that generates sulfonic acid upon exposure into a polymer used in a resist composition. This method of suppressing acid diffusion by introducing such a repeating unit that generates acid upon exposure into a base polymer is effective as a method for obtaining a pattern with a small LER. However, such a base polymer containing a repeating unit that generates acid upon exposure may also have problems with solubility in organic solvents due to the structure and introduction rate of the unit.

[0007] A large number of polymers having an aromatic skeleton with an acidic side chain, such as polyhydroxystyrene, are useful as base polymers for KrF lithography resist compositions, but are not used as base polymers for ArF lithography resist compositions because they exhibit large absorption of light with a wavelength of around 200 nm. However, they are important materials from the viewpoint of obtaining high etching resistance for EB lithography resist compositions and EUV lithography resist compositions, which are powerful technologies for forming patterns smaller than the processing limit of ArF excimer lasers.

[0008] As for the base polymer of positive EB photolithography resist composition and EUV photolithography resist composition, the acid generated by irradiating high-energy rays to the photoacid generator is mainly used as a catalyst, and the acid-labile group shielding the acidic functional group of the phenol side chain possessed by the base polymer is deprotected, thereby making the material soluble in the alkaline developer. In addition, as for the aforementioned acid-labile group, tertiary alkyl, tert-butoxycarbonyl, acetal group, etc. are mainly used. Here, if an acid-labile group with a small activation energy required for deprotection is used, such as an acetal group, there is an advantage that a highly sensitive resist film can be obtained, but when the diffusion of the generated acid is not sufficiently suppressed, a deprotection reaction will also occur in the unexposed part of the resist film, resulting in the problem of degradation of resolution and LER.

[0009] On the other hand, in the development step of photomask manufacturing, it is known that a phenomenon called development load occurs, in which a difference in the size of the pattern in the denser and sparser areas of the photomask occurs. That is, due to the development load, the size of the pattern will be unevenly distributed according to the distribution of the surrounding patterns. As for its main causes, there can be cited differences in the release reaction when the acid is generated due to the energy difference of EB, and differences in the dissolution rate of the dense and sparse pattern drawing parts to the alkaline developer. As for one of its improvements, in order to correct the development load, there is a method in Patent Document 4 that adjusts the incident dose in the EB drawing device and irradiates EB to draw a pattern on the photomask. However, the known correction method is not a correction that fully considers the phenomenon of development load. Therefore, the correction accuracy of the development load of the known correction method is not good. In order to solve this problem, some people have developed methods described in Patent Documents 5 and 6 to improve the drawing method when drawing the resist film and the development method after patterning. However, it is not sufficient to evenly distribute sparse and dense fine patterns in the advanced generation, and improvements in the resist composition are desired.

[0010] Prior art literature

[0011] Patent Literature

[0012] [Patent Document 1] Japanese Patent Application Publication No. 2009-53518

[0013] [Patent Document 2] Japanese Patent Application Publication No. 2010-100604

[0014] [Patent Document 3] Japanese Patent Application Publication No. 2011-22564

[0015] [Patent Document 4] Japanese Patent Application Publication No. 2007-150243

[0016] [Patent Document 5] Japanese Patent No. 5443548

[0017] [Patent Document 6] Japanese Patent No. 6281244 Summary of the invention

[0018] [Problems to be solved by the invention]

[0019] The present invention is made to solve the above-mentioned problems, and its purpose is to provide: a chemically amplified positive resist composition that can form a resist film with extremely high resolution, small LER, excellent rectangularity, and suppressed development load and development residue defects, as well as a resist pattern forming method using the chemically amplified positive resist composition.

[0020] [Methods to solve the problem]

[0021] The inventors of the present application have conducted intensive research to achieve the aforementioned objectives, and have discovered that by introducing a base polymer having a repeating unit in which a phenolic hydroxyl group is protected by a tertiary ether type acid-labile group, and an acid generator that generates a fluorinated aromatic sulfonic acid, into a resist composition, a pattern that exhibits good resolution, pattern shape, and LER, and in which the influence of development load and development residue defects are suppressed, can be obtained, thereby completing the present invention.

[0022] That is, the present invention provides the following chemically amplified positive resist composition and resist pattern forming method.

[0023] 1. A chemically amplified positive resist composition comprising:

[0024] (A) a photoacid generator represented by the following formula (A) which generates an acid due to the action of high-energy rays; and

[0025] (B) a base polymer comprising a polymer having a repeating unit represented by the following formula (B1) whose solubility in an aqueous alkaline solution is increased by the action of an acid;

[0026] [Chemistry 1]

[0027]

[0028] wherein n1 and n2 are each independently an integer of 0 to 2; n3 is an integer of 1≤n3≤4 when n2=0, an integer of 1≤n3≤6 when n2=1, and an integer of 1≤n3≤8 when n2=2; n4 is an integer of 0≤n4≤3 when n2=0, an integer of 0≤n4≤5 when n2=1, and an integer of 0≤n4≤7 when n2=2; but n3+n4 is 1≤n3+n4≤4 when n2=0, 1≤n3+n4≤6 when n2=1, and 1≤n3+n4≤8 when n2=2; n5 is an integer of 1≤n5≤5 when n1=0, an integer of 1≤n5≤7 when n1=1, and an integer of 1≤n5≤9 when n1=2;

[0029] R 1 is an iodine atom, or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 and L A The carbon atoms to which the carbon atom is bonded are bonded to adjacent carbon atoms; and when n5 is 2 or more, multiple R 1 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded;

[0030] R 2 is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and when n4 is 2 or more, a plurality of R 2 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded;

[0031] R F1 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated thioalkoxy group having 1 to 6 carbon atoms;

[0032] L A and L B each independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond;

[0033] X L is a single bond or an alkylene group having 1 to 40 carbon atoms which may contain a hetero atom;

[0034] Z + is an onium cation;

[0035] [Chemistry 2]

[0036]

[0037] In the formula, a1 is an integer of 0 to 2; a2 is an integer of 1 or 2; a3 is an integer of 1 or 2; a4 is an integer of 0 to 4;

[0038] R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0039] X 1 is a single bond or *-C(=O)-O-; * represents an atomic bond to a carbon atom of the main chain;

[0040] R AL It is an acid-labile group;

[0041] R F2 is a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxy group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms;

[0042] R 11 is a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom;

[0043] Again, when a2 = 1, -OR AL and-R F2 must be bonded to adjacent carbon atoms on the aromatic ring; then, when a2 = 2, the two -OR AL One of them must be bonded to -R F2 The carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded.

[0044] 2. The chemically amplified positive resist composition of 1, wherein the photoacid generator is represented by the following formula (A1);

[0045] [Chemistry 3]

[0046]

[0047] In the formula, n1~n5, R 1 , R 2 , R F1 , L A , X L and Z + Same as above.

[0048] 3. The chemically amplified positive resist composition of 1 or 2, wherein Z + It is a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2);

[0049] [Chemistry 4]

[0050]

[0051] In the formula, R ct1 ~R ct5 are each independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom; and R ct1 and R ct2 They may also bond to each other to form a ring together with the sulfur atom to which they are bonded.

[0052] 4. The chemically amplified positive resist composition according to any one of 1 to 3, wherein R AL A group represented by the following formula (AL-1) or (AL-2);

[0053] [Chemistry 5]

[0054]

[0055] In the formula, R L1 , R L2 and R L3 Each is independently a hydrocarbon group having 1 to 12 carbon atoms, and a part of -CH2- in the hydrocarbon group may be substituted by -O- or -S-. When the hydrocarbon group contains an aromatic ring, a part or all of the hydrogen atoms in the aromatic ring may be substituted by a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms which may also contain a halogen atom, or an alkoxy group having 1 to 4 carbon atoms which may also contain a halogen atom. In addition, R L1 and R L2 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded;

[0056] R L4 and R L5 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R L6is a hydrocarbon group having 1 to 20 carbon atoms, wherein a portion of the -CH2- in the hydrocarbon group may be substituted by -O- or -S-; and R L5 and R L6 They can also bond to each other and to the carbon atoms and X 2 Together they form a heterocyclic group having 3 to 20 carbon atoms, wherein a portion of the -CH2- in the heterocyclic group may be substituted by -O- or -S-;

[0057] X 2 is -O- or -S-;

[0058] m1 and m2 are each independently 0 or 1;

[0059] * indicates a bond to an adjacent -O- atom.

[0060] 5. The chemically amplified positive resist composition according to any one of 1 to 4, wherein the polymer further comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B2) and a repeating unit represented by the following formula (B3);

[0061] [Chemistry 6]

[0062]

[0063] In the formula, b1 is 0 or 1; b2 is an integer from 0 to 2; b3 is an integer satisfying 0≤b3≤5+2(b2)-b4; b4 is an integer from 1 to 3; b5 is 0 or 1;

[0064] c1 is an integer from 0 to 2; c2 is an integer from 0 to 2; c3 is an integer from 0 to 5; c4 is an integer from 0 to 2;

[0065] R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0066] A 1 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated alkylene group may be substituted by -O-;

[0067] A 2 is a single bond, phenylene, naphthylene or *-C(=O)-OA 21 -;A 21 It is an aliphatic alkylene group having 1 to 20 carbon atoms which may contain a hydroxyl group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group; * represents an atomic bond to a carbon atom of the main chain;

[0068] R 12 is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarboncarbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom;

[0069] R 13 and R 14 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and R 13 and R 14 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded;

[0070] R 15 Each is independently a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms;

[0071] R 16 Each is independently a hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom;

[0072] X is an acid-labile group when b4 is 1, and is a hydrogen atom or an acid-labile group when b4 is 2 or 3, but at least one of them is an acid-labile group.

[0073] 6. The chemically amplified positive resist composition according to any one of 1 to 5, wherein the polymer further comprises a repeating unit represented by the following formula (B4);

[0074] [Chemistry 7]

[0075]

[0076] Wherein, d1 is an integer satisfying 0≤d1≤5+2(d3)-d2; d2 is an integer from 1 to 3; d3 is an integer from 0 to 2;

[0077] R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0078] Y 1 is a single bond, *-C(=O)-O- or *-C(=O)-NH-; * represents an atomic bond to a carbon atom of the main chain;

[0079] A 3 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a portion of the -CH2- of the saturated alkylene group may be substituted by -O-;

[0080] R 21 It is a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom.

[0081] 7. The chemically amplified positive resist composition according to any one of 1 to 6, wherein the polymer comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B5), a repeating unit represented by the following formula (B6), and a repeating unit represented by the following formula (B7);

[0082] [Chemistry 8]

[0083]

[0084] In the formula, e is an integer of 0 to 6; f is an integer of 0 to 4; g1 is 0 or 1; g2 is an integer of 0 to 2; g3 is an integer of 0 to 5;

[0085] R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0086] R 22 and R 23 Each is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom;

[0087] R 24 is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbonoxy group having 1 to 20 carbon atoms, a saturated hydrocarboncarbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbonoxyalkyl group having 2 to 20 carbon atoms, a saturated hydrocarbonthioalkyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group or a cyano group, and when g2 is 1 or 2, it may also be a hydroxyl group;

[0088] A 4 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of the -CH2- of the saturated alkylene group may be substituted by -O-.

[0089] 8. The chemically amplified positive resist composition according to any one of 1 to 7, wherein the polymer further comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B8), a repeating unit represented by the following formula (B9), a repeating unit represented by the following formula (B10), and a repeating unit represented by the following formula (B11);

[0090] [Chemistry 9]

[0091]

[0092] In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0093] Z 1 is a single bond or a phenylene group;

[0094] Z 2 for* 1 -C(=O)-OZ 21 -, * 1 -C(=O)-NH-Z 21 -or* 1 -OZ21 -;Z 21 An aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group;* 1 Represents Z 1 Atomic bonds;

[0095] Z 3 Each independently represents a single bond, phenylene, naphthylene or * 2 -C(=O)-OZ 31 -;Z 31 is an aliphatic alkylene group having 1 to 10 carbon atoms, a phenylene group or a naphthylene group, and the aliphatic alkylene group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring;* 2 represents the atomic bonds to the carbon atoms of the backbone;

[0096] Z 4 Each is independently a single bond, * 3 -Z 41 -C(=O)-O-,* 3 -C(=O)-NH-Z 41 -or* 3 -OZ 41 -;Z 41 is an alkylene group having 1 to 20 carbon atoms which may contain heteroatoms; * 3 Represents Z 3 Atomic bonds;

[0097] Z 5 Each is independently a single bond, * 4 -Z 51 -C(=O)-O-,* 4 -C(=O)-NH-Z 51 -or* 4 -OZ 51 -;Z 51 is an alkylene group having 1 to 20 carbon atoms which may contain heteroatoms; * 4 Represents Z 4 Atomic bonds;

[0098] Z 6 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, * 2 -C(=O)-OZ 61 -, * 2 -C(=O)-N(H)-Z 61 -or* 2 -OZ 61 -;Z 61It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group or a phenylene group substituted with a trifluoromethyl group, and may also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group;* 2 represents the atomic bonds to the carbon atoms of the backbone;

[0099] R 31 and R 32 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; and R 31 and R 32 They may also bond to each other and form a ring together with the sulfur atom to which they are bonded;

[0100] L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate bond, a carbonate bond or a carbamate bond;

[0101] R 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms;

[0102] R 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms;

[0103] R 5 and Rf 6 Each independently represents a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; but not all Rf 5 and Rf 6 At the same time, it is a hydrogen atom; M - It is a non-nucleophilic counter ion;

[0104] A + is an onium cation;

[0105] h is an integer from 0 to 3.

[0106] 9. The chemically amplified positive resist composition according to any one of 1 to 8, further comprising an organic solvent.

[0107] 10. The chemically amplified positive resist composition according to any one of 1 to 9, further comprising a fluorine-containing polymer containing at least one selected from the group consisting of a repeating unit represented by the following formula (D1), a repeating unit represented by the following formula (D2), a repeating unit represented by the following formula (D3), and a repeating unit represented by the following formula (D4), and further comprising at least one selected from the group consisting of a repeating unit represented by the following formula (D5) and a repeating unit represented by the following formula (D6);

[0108] [Chemistry 10]

[0109]

[0110] In the formula, x is an integer from 1 to 3; y is an integer satisfying 0≤y≤5+2z-x; z is 0 or 1; w is an integer from 1 to 3;

[0111] R B are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;

[0112] R C are each independently a hydrogen atom or a methyl group;

[0113] R 101 , R 102 , R 104 and R 105 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms;

[0114] R 103 , R 106 , R 107 and R 108 are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-labile group, and R 103 , R 106 , R 107 and R 108 When it is a hydrocarbon group or a fluorinated hydrocarbon group, the carbon-carbon bonds may be separated by ether bonds or carbonyl groups;

[0115] R 109 A hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group between carbon-carbon bonds;

[0116] R 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group between carbon-carbon bonds;

[0117] R 111 A saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and a portion of the -CH2- of the saturated hydrocarbon group may be replaced by an ester bond or an ether bond;

[0118] W 1 A (w+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (w+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms;

[0119] W 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-;

[0120] W 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-NH-W31 -W 32 -;W 31 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms; W 32 is a single bond, an ester bond, an ether bond or a sulfonamide bond;

[0121] * indicates atomic bonds to carbon atoms of the main chain.

[0122] 11. The chemically amplified positive resist composition according to any one of 1 to 10, further comprising a quencher.

[0123] 12. The chemically amplified positive resist composition according to any one of 1 to 11, further comprising a photoacid generator other than the photoacid generator represented by formula (A).

[0124] 13. A method for forming a resist pattern, comprising the following steps:

[0125] A resist film is formed on a substrate using the chemically amplified positive resist composition of any one of items 1 to 12; the resist film is exposed using high energy rays; and the exposed resist film is developed using an alkaline developer to obtain a resist pattern.

[0126] 14. The resist pattern forming method according to 13, wherein the high-energy ray is extreme ultraviolet ray or electron beam.

[0127] 15. The resist pattern forming method according to 13 or 14, wherein the outermost surface of the substrate is composed of a material containing at least one selected from chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten and tin.

[0128] 16. The resist pattern forming method according to any one of 13 to 15, wherein the substrate is a transmission type or reflection type blank mask.

[0129] 17. A transmission type or reflection type blank mask coated with the chemically amplified positive resist composition according to any one of 1 to 12.

[0130] [Effects of the Invention]

[0131] The chemically amplified positive resist composition of the present invention can form a pattern with high resolution, low LER, good shape after exposure, excellent rectangularity, and a pattern with suppressed influence of development load, and is suitable as a resist composition for forming a resist film that is sensitive to high-energy rays such as ultraviolet rays, extreme ultraviolet rays, EB, EUV, X-rays, gamma rays, and synchrotron radiation used in the processing of semiconductors, blank photomasks, etc. In addition, the pattern forming method using the chemically amplified positive resist composition of the present invention can form a pattern with high resolution and etching resistance, and a pattern with reduced LER, and a pattern with suppressed influence of development load and development residue defects, so it can be ideally used in micro-processing technology, especially EUV lithography and EB lithography. BRIEF DESCRIPTION OF THE DRAWINGS

[0132] [ Figure 1 ] is the nuclear magnetic resonance spectrum of the photoacid generator PAG-1 synthesized in Synthesis Example 1-1 ( 1 H-NMR / DMSO-d6). DETAILED DESCRIPTION

[0133] [Chemically amplified positive resist composition]

[0134] [(A) Photoacid generator]

[0135] The chemically amplified positive resist composition of the present invention comprises a photoacid generator represented by the following formula (A) as component (A).

[0136] [Chemistry 11]

[0137]

[0138] In formula (A), n1 and n2 are each independently an integer of 0 to 2. n3 is an integer of 1≤n3≤4 when n2=0, an integer of 1≤n3≤6 when n2=1, and an integer of 1≤n3≤8 when n2=2.

[0139] In formula (A), n4 is an integer of 0≤n4≤3 when n2=0, an integer of 0≤n4≤5 when n2=1, and an integer of 0≤n4≤7 when n2=2. However, n3+n4 is 1≤n3+n4≤4 when n2=0, 1≤n3+n4≤6 when n2=1, and 1≤n3+n4≤8 when n2=2.

[0140] In formula (A), n5 is an integer of 1≤n5≤5 when n1=0, an integer of 1≤n5≤7 when n1=1, and an integer of 1≤n5≤9 when n1=2.

[0141] In formula (A), R 1is an iodine atom, or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 Bonded to L A Specific examples of the aforementioned hydrocarbon groups include branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, tert-pentyl, and 2-ethylhexyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, tricyclo[5.2.1.0 2,6 ] aliphatic cyclic hydrocarbon groups having 3 to 20 carbon atoms, such as decyl and adamantyl; aryl groups, such as phenyl, naphthyl, anthracenyl; groups obtained by combining them, etc., but not limited to these. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and part of -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, it may also contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, etc. As for the aforementioned halogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. may be listed, but fluorine atoms or iodine atoms are more ideal. When n5 is 2 or more, each R 1 They can be the same or different.

[0142] When n5 is 2 or more, multiple R 1 They may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. The above-mentioned ring is preferably a 5- to 8-membered ring.

[0143] In formula (A), R 1 The structures formed by bonding with an aromatic ring include the following, but are not limited to these. A of atomic bonds.

[0144] [Chemistry 12]

[0145]

[0146] [Chemistry 13]

[0147]

[0148] [Chemistry 14]

[0149]

[0150] [Chemistry 15]

[0151]

[0152] [Chemistry 16]

[0153]

[0154] [Chemistry 17]

[0155]

[0156] [Chemistry 18]

[0157]

[0158] In formula (A), R 2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0 2,6 ] cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as decyl, adamantyl, adamantylmethyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, etc. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, etc., and part of the -CH2- of the aforementioned hydrocarbon group may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, etc. As a result, it may also contain hydroxyl groups, cyano groups, halogen atoms, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate bonds, lactone rings, sultone rings, carboxylic anhydride (-C(=O)-OC(=O)-), haloalkyl groups, etc. As for the aforementioned halogen atoms, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. may be listed, but fluorine atoms or iodine atoms are more ideal. When n4 is 2 or more, each R 2 They can be the same or different.

[0159] When n4 is 2 or more, multiple R 2 They may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. The above-mentioned ring is preferably a 5- to 8-membered ring.

[0160] In formula (A), R F1 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated thioalkoxy group having 1 to 6 carbon atoms. F1For example, fluorine atom, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio or difluoromethylthio is more preferred, and fluorine atom, trifluoromethyl or trifluoromethoxy is more preferred. By containing fluorine atom, the acid strength of the generated acid will be increased, so the deprotection reaction will proceed smoothly. When n3 is 2 or more, each R F1 They can be the same or different.

[0161] In formula (A), L A and L B Each is independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond. Among them, an ether bond, an ester bond or a sulfonate bond is more preferred, and an ether bond or a sulfonate bond is more preferred.

[0162] In formula (A), X L is a single bond or a alkylene group having 1 to 40 carbon atoms which may contain a hetero atom. The alkylene group may be linear, branched or cyclic, and specific examples thereof include alkanediyl and cyclic saturated alkylene groups. Specific examples of the hetero atom include oxygen, nitrogen and sulfur atoms.

[0163] Just X L Specific examples of the alkylene group having 1 to 40 carbon atoms which may contain a hetero atom represented by the formula include those shown below, but are not limited to these. A and L B of atomic bonds.

[0164] [Chemistry 19]

[0165]

[0166] [Chemistry 20]

[0167]

[0168] [Chemistry 21]

[0169]

[0170] [Chemistry 22]

[0171]

[0172] Among these, X L -0~X L -22 and X L -47~X L -58 is ideal.

[0173] The photoacid generator represented by the formula (A) is preferably represented by the following formula (A1).

[0174] [Chemistry 23]

[0175]

[0176] In the formula, n1~n5, R 1 , R 2 , R F1 , L A , X L and Z + Same as above.

[0177] Specific examples of the anion of the photoacid generator represented by the formula (A) include those shown below, but are not limited to these.

[0178] [Chemistry 24]

[0179]

[0180] [Chemistry 25]

[0181]

[0182] [Chemistry 26]

[0183]

[0184] [Chemistry 27]

[0185]

[0186] [Chemistry 28]

[0187]

[0188] [Chemistry 29]

[0189]

[0190] [Chemistry 30]

[0191]

[0192] [Chemistry 31]

[0193]

[0194] [Chemistry 32]

[0195]

[0196] [Chemistry 33]

[0197]

[0198] [Chemistry 34]

[0199]

[0200] [Chemistry 35]

[0201]

[0202] [Chemistry 36]

[0203]

[0204] [Chemistry 37]

[0205]

[0206] [Chemistry 38]

[0207]

[0208] [Chemistry 39]

[0209]

[0210] [Chemistry 40]

[0211]

[0212] [Chemistry 41]

[0213]

[0214] [Chemistry 42]

[0215]

[0216] [Chemistry 43]

[0217]

[0218] [Chemistry 44]

[0219]

[0220] [Chemistry 45]

[0221]

[0222] [Chemistry 46]

[0223]

[0224] [Chemistry 47]

[0225]

[0226] [Chemistry 48]

[0227]

[0228] [Chemistry 49]

[0229]

[0230] [Chemistry 50]

[0231]

[0232] [Chemistry 51]

[0233]

[0234] [Chemistry 52]

[0235]

[0236] [Chemistry 53]

[0237]

[0238] [Chemistry 54]

[0239]

[0240] [Chemistry 55]

[0241]

[0242] In formula (A), Z + The onium cation is preferably a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2).

[0243] [Chemistry 56]

[0244]

[0245] In formula (cation-1) and (cation-2), R ct1 ~R ct5 Each is independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom.

[0246] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0247] The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 30 carbon atoms, such as cyclohexenyl; aryl groups having 6 to 30 carbon atoms, such as phenyl, naphthyl, and thienyl; aralkyl groups having 7 to 30 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, but aryl groups are more preferred. Furthermore, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a part of the -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing hetero atoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain a hydroxyl group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, and the like.

[0248] Again, R ct1 and R ct2 They may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, examples of the ring include those represented by the following formula.

[0249] [Chemistry 57]

[0250]

[0251] In the formula, the dotted line represents the ct3 of atomic bonds.

[0252] Examples of the sulfonium cation represented by the formula (cation-1) include the following, but are not limited to these.

[0253] [Chemistry 58]

[0254]

[0255] [Chemistry 59]

[0256]

[0257] [Chemistry 60]

[0258]

[0259] [Chemistry 61]

[0260]

[0261] [Chemistry 62]

[0262]

[0263] [Chemistry 63]

[0264]

[0265] [Chemistry 64]

[0266]

[0267] [Chemistry 65]

[0268]

[0269] [Chemistry 66]

[0270]

[0271] [Chemistry 67]

[0272]

[0273] [Chemistry 68]

[0274]

[0275] [Chemistry 69]

[0276]

[0277] [Chemistry 70]

[0278]

[0279] [Chemistry 71]

[0280]

[0281] [Chemistry 72]

[0282]

[0283] [Chemistry 73]

[0284]

[0285] [Chemistry 74]

[0286]

[0287] [Chemistry 75]

[0288]

[0289] [Chemistry 76]

[0290]

[0291] [Chemistry 77]

[0292]

[0293] [Chemistry 78]

[0294]

[0295] [Chemistry 79]

[0296]

[0297] [Chemistry 80]

[0298]

[0299] [Chemistry 81]

[0300]

[0301] [Chemistry 82]

[0302]

[0303] [Chemistry 83]

[0304]

[0305] Examples of the iodonium cation represented by the formula (cation-2) include those shown below, but are not limited to these.

[0306] [Chemistry 84]

[0307]

[0308] [Chemistry 85]

[0309]

[0310] Specific examples of the photoacid generator represented by formula (A) include any combination of the above-mentioned anions and cations.

[0311] In the chemically amplified positive resist composition of the present invention, the content of the (A) photoacid generator is preferably 0.1 to 40 parts by mass, and more preferably 1 to 20 parts by mass relative to 80 parts by mass of the (B) base polymer described later. If the content of the acid generator falls within the above range, an amount of acid necessary for deprotection of the acid-labile group is generated, and the storage stability is also good. The (A) photoacid generator may be used alone or in combination of two or more.

[0312] [(B) Base polymer]

[0313] The chemically amplified positive resist composition of the present invention comprises, as component (B), a base polymer containing a phenolic hydroxyl group protected by an acid-labile group and becoming an alkali-soluble polymer due to the action of an acid.

[0314] The repeating unit in which the phenolic hydroxyl group is protected by an acid-labile group (hereinafter, also referred to as repeating unit B1) is represented by the following formula (B1).

[0315] [Chemistry 86]

[0316]

[0317] In formula (B1), a1 is an integer of 0 to 2. When a1 is 0, it is a benzene ring, when a1 is 1, it is a naphthalene ring, and when a1 is 2, it is an anthracene ring. Considering the solubility in the solvent, a benzene ring in which a1 is 0 is more preferable. a2 is an integer of 1 or 2, but considering the supply of raw materials, a2 is more preferably 1. a3 is an integer of 1 or 2, but considering the supply of raw materials, a3 is more preferably 1. a4 is an integer of 0 to 4, but considering the supply of raw materials, a4 is more preferably 0 or 1.

[0318] In formula (B1), R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0319] In formula (B1), X 1 is a single bond or *-C(=O)-O-. * represents an atomic bond to a carbon atom of the main chain. 1 A single bond is ideal.

[0320] In formula (B1), R AL is an acid-labile group. When a2 is 2, each R AL The acid-labile group is preferably a group represented by the following formula (AL-1) or (AL-2).

[0321] [Chemistry 87]

[0322]

[0323] In the formula, * represents an atomic bond with an adjacent oxygen atom.

[0324] In formula (AL-1), R L1 , R L2 and R L3Each is independently a hydrocarbon group having 1 to 12 carbon atoms, a part of the -CH2- of the hydrocarbon group may be substituted by -O- or -S-, and when the hydrocarbon group contains an aromatic ring, a part or all of the hydrogen atoms of the aromatic ring may be substituted by an alkyl group having 1 to 4 carbon atoms which may also contain a halogen atom, a cyano group, a nitro group, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms which may also contain a halogen atom.

[0325] R L1 , R L2 and R L3 The hydrocarbon group having 1 to 12 carbon atoms represented by may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, norbornylmethyl, adamantyl, adamantylmethyl, tricyclo[5.2.1.0 2,6 ]decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 ] Cyclic saturated hydrocarbon groups having 3 to 12 carbon atoms, such as dodecyl; alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl; alkynyl groups having 2 to 12 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, hexynyl; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 12 carbon atoms, such as cyclopentenyl and cyclohexenyl; aryl groups having 6 to 12 carbon atoms, such as phenyl, naphthyl, indanyl; aralkyl groups having 7 to 12 carbon atoms, such as benzyl, 1-phenylethyl, 2-phenylethyl: groups obtained by combining these, etc.

[0326] Again, R L1 and R L2 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring formed in this case include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornane ring, an adamantane ring, a tricyclo[5.2.1.0 2,6 ]Decane ring, tetracyclic [6.2.1.1 3,6 .0 2,7 ] dodecane ring, etc. In addition, a part of -CH2- in the aforementioned ring may be substituted by -O- or -S-.

[0327] In formula (AL-2), R L4 and R L5 Each R is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. L4 and R L5The hydrocarbon group having 1 to 10 carbon atoms represented by may be saturated or unsaturated, and may be straight chain, branched, or cyclic. L1 , R L2 and R L3 Among the exemplified hydrocarbon groups having 1 to 12 carbon atoms represented by , those having 1 to 10 carbon atoms are the same.

[0328] In formula (AL-2), R L6 It is a hydrocarbon group having 1 to 20 carbon atoms, and a part of -CH2- of the hydrocarbon group may be substituted by -O- or -S-. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.; cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, norbornylmethyl, adamantyl, adamantylmethyl, tricyclo[5.2.1.0 2,6 ]decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 ] Cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as dodecyl; alkenyl groups having 2 to 20 carbon atoms, such as ethenyl, propenyl, butenyl, pentenyl, and hexenyl; alkynyl groups having 2 to 20 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, and hexynyl; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopentenyl, cyclohexenyl, and norbornyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, and tert-butylnaphthyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenethyl; groups obtained by combining them, etc.

[0329] Again, R L5 and R L6 They can also be bonded to each other and to the carbon atoms and X 2 Together they form a heterocyclic group having 3 to 20 carbon atoms, and a portion of -CH2- in the heterocyclic group may be substituted by -O- or -S-.

[0330] In formula (AL-2), X 2 It is -O- or -S-.

[0331] In formula (AL-1) and (AL-2), m1 and m2 are each independently 0 or 1.

[0332] Examples of the acid-labile group represented by the formula (AL-1) include, but are not limited to, the following. In the following formula, * represents an atomic bond with an adjacent -O- group.

[0333] [Chemistry 88]

[0334]

[0335] [Chemistry 89]

[0336]

[0337] [Chemistry 90]

[0338]

[0339] [Chemistry 91]

[0340]

[0341] [Chemistry 92]

[0342]

[0343] [Chemistry 93]

[0344]

[0345] [Chemistry 94]

[0346]

[0347] [Chemistry 95]

[0348]

[0349] [Chemistry 96]

[0350]

[0351] [Chemistry 97]

[0352]

[0353] [Chemistry 98]

[0354]

[0355] Examples of the acid-labile group represented by the formula (AL-2) include, but are not limited to, the following. In the following formula, * represents an atomic bond with an adjacent oxygen atom.

[0356] [Chemistry 99]

[0357]

[0358] [Chemical 100]

[0359]

[0360] In formula (B1), R F2 is a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxy group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms. F2 For example, fluorine atoms, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio or difluoromethylthio are more preferred, and fluorine atoms, trifluoromethyl or trifluoromethoxy are more preferred. In particular, by containing fluorine atoms, a pattern with strong anti-collapse effect can be formed due to the swelling inhibition effect. When a3 is 2 or more, each R F2 They can be the same or different.

[0361] In formula (B1), -OR AL and-R F2 There must be one or more groups of atoms bonded to adjacent carbon atoms on the aromatic ring. That is, when a2 = 1, -OR AL and-R F2 When adjacent carbon atoms on the aromatic ring are bonded to each other, a2 = 2, two -OR AL At least one of them is bonded to -R F2 The carbon atoms in the aromatic ring are bonded to adjacent carbon atoms. AL and-R F2 adjacent to each other, in R AL The acidity of the aromatic alcohol generated after deprotection will increase.

[0362] In formula (B1), R 11It is a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. The hydrocarbon group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups having 6 to 20 carbon atoms, such as phenyl and naphthyl; aralkyl groups having 7 to 20 carbon atoms, such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these. Furthermore, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, a hydroxyl group, a cyano group, a chlorine atom, a bromine atom, an iodine atom, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. may be contained. When a4 is 2 or more, each R 11 They can be the same or different.

[0363] The monomers providing the repeating unit B1 include the following, but are not limited thereto. AL and-R F2 If they are arranged adjacent to each other, they are not limited to this. A Same as above.

[0364] [Chemistry 101]

[0365]

[0366] [Chemistry 102]

[0367]

[0368] [Chemistry 103]

[0369]

[0370] [Chemistry 104]

[0371]

[0372] [Chemistry 105]

[0373]

[0374] [Chemistry 106]

[0375]

[0376] [Chemistry 107]

[0377]

[0378] [Chemistry 108]

[0379]

[0380] [Chemistry 109]

[0381]

[0382] [Chemistry 110]

[0383]

[0384] [Chemistry 111]

[0385]

[0386] [Chemistry 112]

[0387]

[0388] [Chemistry 113]

[0389]

[0390] [Chemistry 114]

[0391]

[0392] [Chemistry 115]

[0393]

[0394] [Chemistry 116]

[0395]

[0396] [Chemistry 117]

[0397]

[0398] [Chemistry 118]

[0399]

[0400] [Chemistry 119]

[0401]

[0402] [Chemistry 120]

[0403]

[0404] [Chemistry 121]

[0405]

[0406] [Chemistry 122]

[0407]

[0408] [Chemistry 123]

[0409]

[0410] [Chemistry 124]

[0411]

[0412] [Chemistry 125]

[0413]

[0414] [Chemistry 126]

[0415]

[0416] [Chemistry 127]

[0417]

[0418] [Chemistry 128]

[0419]

[0420] [Chemistry 129]

[0421]

[0422] [Chemistry 130]

[0423]

[0424] [Chemistry 131]

[0425]

[0426] [Chemistry 132]

[0427]

[0428] [Chemistry 133]

[0429]

[0430] [Chemistry 134]

[0431]

[0432] [Chemistry 135]

[0433]

[0434] The polymer may further contain at least one selected from the group consisting of a repeating unit represented by the following formula (B2) (hereinafter, also referred to as repeating unit B2) and a repeating unit represented by the following formula (B3) (hereinafter, also referred to as repeating unit B3).

[0435] [Chemistry 136]

[0436]

[0437] In formula (B2), b1 is 0 or 1. b2 is an integer of 0 to 2, and when 0, it represents a benzene skeleton, when 1, it represents a naphthalene skeleton, and when 2, it represents an anthracene skeleton. b3 is an integer satisfying 0≤b3≤5+2(b2)-b4. b4 is an integer of 1 to 3. b5 is 0 or 1. When b2 is 0, it is more preferable that b3 is an integer of 0 to 3 and b4 is an integer of 1 to 3. When b2 is 1 or 2, it is more preferable that b3 is an integer of 0 to 4 and b4 is an integer of 1 to 3.

[0438] In formula (B3), c1 is an integer of 0 to 2. c2 is an integer of 0 to 2. c3 is an integer of 0 to 5. c4 is an integer of 0 to 2.

[0439] In formula (B2) and (B3), R A Each is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0440] In formula (B2), A 1is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of -CH2- of the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be linear, branched or cyclic. Specific examples thereof include alkylene groups such as methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers; cyclic saturated alkylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them. In the case where the saturated alkylene group includes an ether bond, when b1 in formula (B2) is 1, it may be inserted anywhere except between the carbon atom at the α position and the carbon atom at the β position relative to the ester oxygen atom. When b1 is 0, the atom bonded to the main chain becomes an etheric oxygen atom, and the second ether bond may be inserted in a position other than between the carbon atom at the α position and the carbon atom at the β position relative to the etheric oxygen atom. In addition, if the carbon number of the saturated alkylene group is 10 or less, sufficient solubility in an alkaline developer can be obtained, which is more preferable.

[0441] In formula (B3), A 2 is a single bond, phenylene, naphthylene or *-C(=O)-OA 21 -.A 21 It is an aliphatic alkylene group having 1 to 20 carbon atoms which may contain a hydroxyl group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group. * represents an atomic bond to a carbon atom of the main chain.

[0442] In formula (B2), R 12 It is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom. The saturated hydrocarbon group, the saturated hydrocarbon oxy group, and the saturated hydrocarbon carbonyloxy group may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, and hexyl; cycloalkyl groups having 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in alkaline developer is good. When b3 is 2 or more, each R 12 They can be the same or different.

[0443] In formula (B3), R 13 and R 14 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, R 13 and R 14 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

[0444] In formula (B3), R 15Each independently represents a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms. 15 They can be the same or different.

[0445] In formula (B3), R 16 Each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom. 16 They can be the same or different.

[0446] In formula (B2), X is an acid-labile group when b4 is 1, and is a hydrogen atom or an acid-labile group when b4 is 2 or 3, but at least one of them is an acid-labile group. That is, in repeating unit B2, at least one of the phenolic hydroxyl groups bonded to the aromatic ring is protected by an acid-labile group, or the carboxyl group bonded to the aromatic ring is protected by an acid-labile group. As for such an acid-labile group, any one that is used in many known chemically amplified positive resist compositions and that is separated by acid to provide an acidic group can be used without particular limitation.

[0447] If a saturated tertiary hydrocarbon group is selected as the acid-labile group, it is more ideal because it can provide a pattern with a small LER when forming a film with a resist film thickness of, for example, 10 to 100 nm and forming a fine pattern with a line width of 45 nm or less. As for the tertiary alkyl group, it is more ideal to have 4 to 18 carbon atoms in order to obtain the resulting polymerization monomer by distillation. In addition, as for the group bonded to the tertiary carbon atom of the saturated tertiary hydrocarbon group, there can be mentioned a saturated hydrocarbon group with 1 to 15 carbon atoms which may also contain an oxygen-containing functional group such as an ether bond or a carbonyl group, and the groups bonded to the tertiary carbon atom may also be bonded to each other to form a ring.

[0448] Specific examples of the group bonded to the tertiary carbon atom include methyl, ethyl, propyl, adamantyl, norbornyl, tetrahydrofuran-2-yl, 7-oxanorbornane-2-yl, cyclopentyl, 2-tetrahydrofuranyl, tricyclo[5.2.1.0 2,6 ]decyl, tetracyclic [4.4.0.1 2,5 .1 7,10 ]dodecyl, 3-oxo-1-cyclohexyl.

[0449] Examples of the saturated tertiary hydrocarbon groups having these as substituents include tert-butyl, tert-amyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 1,1,2-trimethylpropyl, 1-adamantyl-1-methylethyl, 1-methyl-1-(2-norbornyl)ethyl, 1-methyl-1-(tetrahydrofuran-2-yl)ethyl, 1-methyl-1-(7-oxanorbornan-2-yl)ethyl, 1-methylcyclopentyl, , 1-ethylcyclopentyl, 1-propylcyclopentyl, 1-isopropylcyclopentyl, 1-cyclopentylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(2-tetrahydrofuranyl)cyclopentyl, 1-(7-oxanorbornan-2-yl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-cyclopentylcyclohexyl, 1-cyclohexylcyclohexyl, 2-methyl-2-norbornyl, 2-ethyl-2-norbornyl, 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, 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, but are not limited to these.

[0450] In addition, as the aforementioned acid-labile group, a group represented by the following formula (B2-1) can be cited. The group represented by formula (B2-1) is often used as an acid-labile group, and is a useful option for providing a pattern with a relatively rectangular interface between the pattern and the substrate. When X is a group represented by formula (B2-1), an acetal structure is formed.

[0451] [Chemistry 137]

[0452]

[0453] In the formula, the dotted lines represent atomic bonds.

[0454] In formula (B2-1), R L11 R is a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. L12 It is a saturated hydrocarbon group having 1 to 30 carbon atoms. The saturated hydrocarbon group may be linear, branched or cyclic.

[0455] R L11It is appropriately selected according to the design of the sensitivity of the acid-degradable group. For example, if it is designed to be decomposed by a strong acid in order to ensure high stability, a hydrogen atom is selected, and if it is designed to be highly sensitive to pH changes using high reactivity, a straight-chain alkyl group is selected. Although it also depends on the combination of the acid generator and the basic compound mixed in the resist composition, it is generally preferred to select a larger alkyl group as R at the end. L12 , and when the solubility change due to decomposition is large, R L11 For example, the carbon atom bonded to the acetal carbon is preferably a secondary carbon atom. L11 Examples of the group include isopropyl, sec-butyl, cyclopentyl, and cyclohexyl.

[0456] Among the above acetal groups, in order to obtain higher resolution, R L12 It is preferably a polycyclic alkyl group having 7 to 30 carbon atoms. L12 When it is a polycyclic alkyl group, it is more preferable to form a bond between a secondary carbon atom constituting the polycyclic ring structure and the acetal oxygen. When it is bonded to a secondary carbon atom of the ring structure, the polymer becomes a stable compound compared to the case of bonding to a tertiary carbon atom, and the storage stability as a resist composition becomes good, and the resolution does not deteriorate. L12 Compared with the case where the polymer is bonded to a primary carbon atom of a linear alkyl group having 1 or more carbon atoms, the glass transition temperature (Tg) of the polymer becomes better, and the shape defect of the resist pattern after development due to baking does not occur.

[0457] Preferred examples of the group represented by formula (B2-1) include those shown below, but are not limited to these. L11 As before, dashed lines represent atomic bonds.

[0458] [Chemistry 138]

[0459]

[0460] Preferred examples of repeating unit B3 include those shown below, but are not limited to these. A Same as above.

[0461] [Chemistry 139]

[0462]

[0463] As the acid-labile group, a phenolic hydroxyl group may be substituted with -CH2COO- (a saturated tertiary hydrocarbon group) for the hydrogen atom of the phenolic hydroxyl group. In this case, the saturated tertiary hydrocarbon group may be the same as the saturated tertiary hydrocarbon group used for the protection of the phenolic hydroxyl group.

[0464] The repeating unit B1 is preferably introduced in the range of 4 to 40 mol % among all the repeating units of the polymer contained in the base polymer, and at least one selected from the repeating units B2 and B3 is preferably introduced in the range of 2 to 40 mol % among all the repeating units of the polymer contained in the base polymer. The repeating units B1, B2 and B3 are preferably introduced in the range of 8 to 60 mol % among all the repeating units of the polymer contained in the base polymer, more preferably 10 to 50 mol %, and even more preferably 10 to 40 mol %.

[0465] The aforementioned polymer may further contain a repeating unit represented by the following formula (B4) (hereinafter, also referred to as repeating unit B4).

[0466] [Chemistry 140]

[0467]

[0468] In formula (B4), d1 is an integer satisfying 0≤d1≤5+2(d3)-d2. d2 is an integer of 1 to 3. d3 is an integer of 0 to 2.

[0469] In formula (B4), R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0470] In formula (B4), Y 1 It is a single bond, *-C(=O)-O- or *-C(=O)-NH-. * represents an atomic bond to a carbon atom of the main chain.

[0471] In formula (B4), A 3 It is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a part of -CH2- of the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be straight-chain, branched or cyclic. Specific examples thereof include alkylene groups having 1 to 10 carbon atoms such as methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and their structural isomers; cyclic saturated alkylene groups having 3 to 10 carbon atoms such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl; and groups obtained by combining them.

[0472] In formula (B4), R 21It is a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom. The saturated hydrocarbon group, the saturated hydrocarbon carbonyloxy group, and the saturated hydrocarbon group of the saturated hydrocarbonoxy group may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, and hexyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; and groups obtained by combining them. If the number of carbon atoms is below the upper limit, the solubility in alkaline developer is good. When d1 is 2 or more, each R 21 They can be the same or different.

[0473] Y 1 and A 3 When they are single bonds at the same time, preferred examples of repeating unit B4 include units derived from 3-hydroxystyrene, 4-hydroxystyrene, 5-hydroxy-2-vinylnaphthalene, 6-hydroxy-2-vinylnaphthalene, etc. Among these, more preferred are repeating units represented by the following formula (B4-1).

[0474] [Chemistry 141]

[0475]

[0476] In the formula, R A and d2 are the same as above.

[0477] Y 1 When R is other than a single bond, the preferred examples of repeating unit B4 include those shown below, but are not limited to these. A Same as above.

[0478] [Chemistry 142]

[0479]

[0480] [Chemistry 143]

[0481]

[0482] The repeating unit B4 is preferably introduced in the range of 10 to 95 mol % of all the repeating units of the polymer contained in the base polymer, and more preferably introduced in the range of 30 to 85 mol %. However, when at least one of the repeating units represented by the formula (B5) and the repeating units represented by the formula (B6) described later, which provide the polymer with higher etching resistance, is contained, and the units have a phenolic hydroxyl group as a substituent, it is more preferable to add the proportions thereof and still set them within the aforementioned range. The repeating unit B4 may be used alone or in combination of two or more.

[0483] The polymer contained in the aforementioned base polymer may also contain at least one selected from the repeating unit represented by the following formula (B5) (hereinafter, also referred to as repeating unit B5), the repeating unit represented by the following formula (B6) (hereinafter, also referred to as repeating unit B6) and the repeating unit represented by the following formula (B7) (hereinafter, also referred to as repeating unit B7).

[0484] [Chemistry 144]

[0485]

[0486] In formula (B5) and (B6), e is an integer of 0-6. f is an integer of 0-4.

[0487] In formula (B5) and (B6), R 22 and R 23 Each of them is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom. The saturated hydrocarbon carbonyloxy group, saturated hydrocarbon group, and saturated hydrocarbonoxy group may be linear, branched, or cyclic. When e is 2 or more, each R 22 They may be the same or different from each other. When f is 2 or more, each R 23 They can be the same or different.

[0488] In formula (B7), R A Same as above. g1 is an integer of 0 to 5. g2 is an integer of 0 to 2. g3 is an integer of 0 to 5.

[0489] In formula (B7), R 24 is an acetyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbon oxy group having 1 to 20 carbon atoms, a saturated hydrocarbon carbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbon oxyalkyl group having 2 to 20 carbon atoms, a saturated hydrocarbon thioalkyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group or a cyano group. When g2 is 1 or 2, it may be a hydroxyl group. The saturated hydrocarbon group, saturated hydrocarbon oxy group, saturated hydrocarbon carbonyloxy group, saturated hydrocarbon oxyalkyl group and saturated hydrocarbon thioalkyl group may be straight-chain, branched or cyclic. When g3 is 2 or more, each R 24 They can be the same or different.

[0490] In formula (B7), A 4 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, and a portion of the -CH2- in the saturated alkylene group may be substituted by -O-. The saturated alkylene group may be linear, branched, or cyclic. Specific examples thereof include: 1 Those exemplified in the description of are the same.

[0491] When repeating units B5 to B7 are used, in addition to the etching resistance of the aromatic ring, an effect of improving the EB irradiation resistance during etching and pattern inspection by adding a ring structure to the main chain can be obtained.

[0492] In order to obtain the effect of improving etching resistance, repeating units B5 to B7 are preferably introduced at 5 mol% or more in all repeating units of the polymer contained in the base polymer. In addition, repeating units B5 to B7 are preferably introduced at 30 mol% or less in all repeating units of the polymer contained in the base polymer, and more preferably introduced at 25 mol% or less. In the case of no functional group or the case where the functional group is other than hydroxyl group, if the introduction amount is 30 mol% or less, there is no concern of development defects, so it is more ideal. Repeating units B5 to B7 can be used alone or in combination of two or more.

[0493] Among all the repeating units of the polymer contained in the aforementioned base polymer, the content of repeating unit B4 and at least one selected from repeating units B5 to B7 is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 65 mol% or more, thereby achieving good etching resistance particularly during mask processing.

[0494] The polymer contained in the aforementioned base polymer may further contain at least one selected from the repeating unit represented by the following formula (B8) (hereinafter, also referred to as repeating unit B8), the repeating unit represented by the following formula (B9) (hereinafter, also referred to as repeating unit B9), the repeating unit represented by the following formula (B10) (hereinafter, also referred to as repeating unit B10), and the repeating unit represented by the following formula (B11) (hereinafter, also referred to as repeating unit B11).

[0495] [Chemistry 145]

[0496]

[0497] In formulas (B8) to (B11), R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 1 is a single bond or a phenylene group. 2 for* 1 -C(=O)-OZ 21 -, * 1 -C(=O)-NH-Z 21 -or* 1 -OZ 21 -.Z 21 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may further contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 1 Represents Z1 Atomic bonds. 3 Each independently represents a single bond, phenylene, naphthylene or * 2 -C(=O)-OZ 31 -.Z 31 It is an aliphatic alkylene group having 1 to 10 carbon atoms, a phenylene group or a naphthylene group, and the aliphatic alkylene group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring. 2 Represents an atomic bond to a carbon atom of the main chain. 4 Each is independently a single bond, * 3 -Z 41 -C(=O)-O-,* 3 -C(=O)-NH-Z 41 -or* 3 -OZ 41 -.Z 41 It is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 3 Represents Z 3 Atomic bonds. 5 Each is independently a single bond, * 4 -Z 51 -C(=O)-O-,* 4 -C(=O)-NH-Z 51 -or* 4 -OZ 51 -.Z 51 It is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 4 Represents Z 4 Atomic bonds. 6 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, * 2 -C(=O)-OZ 61 -, * 2 -C(=O)-N(H)-Z 61 -or* 2 -OZ 61 -.Z 61 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 2 Represents atomic bonds to carbon atoms of the backbone chain.

[0498] Z 21 , Z 31 and Z 61The aliphatic alkylene group represented may be straight-chain, branched or cyclic, and specific examples thereof include alkanediyl groups such as methane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl, 1,1-dimethylethane-1,2-diyl, pentane-1,5-diyl, 2-methylbutane-1,2-diyl and hexane-1,6-diyl; cycloalkanediyl groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl and cyclohexanediyl; and groups obtained by combining these groups.

[0499] Z 41 and Z 51 The alkylene group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include those shown below, but are not limited to these.

[0500] [Chemistry 146]

[0501]

[0502] In the formula, the dotted lines represent atomic bonds.

[0503] In formula (B8), R 31 and R 32 Each is independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl; cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl; cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, such as cyclohexenyl; aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, and thienyl; aralkyl groups such as benzyl, 1-phenylethyl, and 2-phenylethyl; and groups obtained by combining these groups, but aryl groups are more preferred. Furthermore, a part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing hetero atoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and a part of the -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing hetero atoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. As a result, it may contain a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, and the like.

[0504] Again, R31 and R 32 They may also be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring may be exemplified by the same as in the description of formula (cation-1) with respect to R ct1 and R ct2 The rings that can be formed by bonding with the sulfur atom to which they are bonded are the same as those exemplified.

[0505] Specific examples of the cation of the repeating unit B8 include those shown below, but are not limited to these. A Same as above.

[0506] [Chemistry 147]

[0507]

[0508] [Chemistry 148]

[0509]

[0510] [Chemistry 149]

[0511]

[0512] [Chemistry 150]

[0513]

[0514] [Chemistry 151]

[0515]

[0516] [Chemistry 152]

[0517]

[0518] [Chemistry 153]

[0519]

[0520] In formula (B8), M -It is a non-nucleophilic counter ion. Specific examples of the non-nucleophilic counter ions include halide ions such as chloride ion and bromide ion; fluoroalkyl sulfonate ions such as trifluoromethanesulfonate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; aryl sulfonate ions such as toluenesulfonate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkyl sulfonate ions such as methanesulfonate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion, etc.

[0521] Then, specific examples of the aforementioned non-nucleophilic counter ions include a sulfonate anion represented by the following formula (B8-1) in which the α-position is substituted with a fluorine atom and a sulfonate anion represented by the following formula (B8-2) in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group.

[0522] [Chemistry 154]

[0523]

[0524] In formula (B8-1), R 33 It is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon carbonyloxy group having 2 to 30 carbon atoms, or a hydrocarbon oxycarbonyl group having 2 to 30 carbon atoms, and the hydrocarbon group may also contain a halogen atom, an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbon group portion of the aforementioned hydrocarbon group, hydrocarbon carbonyloxy group, and hydrocarbon oxycarbonyl group may be saturated or unsaturated, and may be straight chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl, heptadecyl, and eicosyl; cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecyl, tetracyclododecylmethyl, and dicyclohexylmethyl; unsaturated aliphatic hydrocarbon groups having 2 to 30 carbon atoms, such as allyl and 3-cyclohexenyl; aryl groups having 6 to 30 carbon atoms, such as phenyl, 1-naphthyl, and 2-naphthyl; aralkyl groups having 7 to 30 carbon atoms, such as benzyl and diphenylmethyl; and groups obtained by combining these.

[0525] In formula (B8-2), R 34 R is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon carbonyl group having 2 to 30 carbon atoms. The hydrocarbon group and hydrocarbon carbonyl group may contain a halogen atom, an ether bond, an ester bond, a carbonyl group, or a lactone ring. 35is a hydrogen atom, a fluorine atom or a fluorinated alkyl group having 1 to 6 carbon atoms. The hydrocarbon radical of the hydrocarbon radical and hydrocarbon carbonyl group may be saturated or unsaturated, and may be straight chain, branched or cyclic. 33 The hydrocarbon groups represented by are the same as those exemplified above. 35 The trifluoromethyl group is more preferred.

[0526] Specific examples of the sulfonic acid anion represented by formula (B8-1) or (B8-2) include those shown below, but are not limited to these. 35 As mentioned above, Ac is acetyl.

[0527] [Chemistry 155]

[0528]

[0529] [Chemistry 156]

[0530]

[0531] [Chemistry 157]

[0532]

[0533] [Chemistry 158]

[0534]

[0535] [Chemistry 159]

[0536]

[0537] [Chemistry 160]

[0538]

[0539] [Chemistry 161]

[0540]

[0541] [Chemistry 162]

[0542]

[0543] [Chemistry 163]

[0544]

[0545] [Chemistry 164]

[0546]

[0547] Specific examples of the non-nucleophilic counter ion include non-fluorinated sulfonic acid anions. Specific examples thereof include those shown below, but are not limited to these.

[0548] [Chemistry 165]

[0549]

[0550] [Chemistry 166]

[0551]

[0552] [Chemistry 167]

[0553]

[0554] [Chemistry 168]

[0555]

[0556] [Chemistry 169]

[0557]

[0558] [Chemistry 170]

[0559]

[0560] [Chemistry 171]

[0561]

[0562] [Chemistry 172]

[0563]

[0564] [Chemistry 173]

[0565]

[0566] [Chemistry 174]

[0567]

[0568] [Chemistry 175]

[0569]

[0570] [Chemistry 176]

[0571]

[0572] [Chemistry 177]

[0573]

[0574] [Chemistry 178]

[0575]

[0576] [Chemistry 179]

[0577]

[0578] [Chemistry 180]

[0579]

[0580] [Chemistry 181]

[0581]

[0582] [Chemistry 182]

[0583]

[0584] [Chemistry 183]

[0585]

[0586] [Chemistry 184]

[0587]

[0588] [Chemistry 185]

[0589]

[0590] [Chemistry 186]

[0591]

[0592] [Chemistry 187]

[0593]

[0594] [Chemistry 188]

[0595]

[0596] [Chemistry 189]

[0597]

[0598] [Chemistry 190]

[0599]

[0600] [Chemistry 191]

[0601]

[0602] [Chemistry 192]

[0603]

[0604] [Chemistry 193]

[0605]

[0606] [Chemistry 194]

[0607]

[0608] [Chemistry 195]

[0609]

[0610] [Chemistry 196]

[0611]

[0612] [Chemistry 197]

[0613]

[0614] [Chemistry 198]

[0615]

[0616] [Chemistry 199]

[0617]

[0618] [Chemistry 200]

[0619]

[0620] [Chemistry 201]

[0621]

[0622] [Chemistry 202]

[0623]

[0624] [Chemistry 203]

[0625]

[0626] [Chemistry 204]

[0627]

[0628] [Chemistry 205]

[0629]

[0630] [Chemistry 206]

[0631]

[0632] [Chemistry 207]

[0633]

[0634] [Chemistry 208]

[0635]

[0636] [Chemistry 209]

[0637]

[0638] [Chemistry 210]

[0639]

[0640] [Chemistry 211]

[0641]

[0642] [Chemistry 212]

[0643]

[0644] [Chemistry 213]

[0645]

[0646] [Chemistry 214]

[0647]

[0648] [Chemistry 215]

[0649]

[0650] [Chemistry 216]

[0651]

[0652] [Chemistry 217]

[0653]

[0654] [Chemistry 218]

[0655]

[0656] In formula (B9) and (B10), L 1It is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate bond, a carbonate bond or a carbamate bond. Among these, an ether bond, an ester bond or a carbonyl group is preferred from the viewpoint of synthesis, and an ester bond or a carbonyl group is more preferred.

[0657] In formula (B9), Rf 1 and Rf 2 Each independently represents a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. 1 and Rf 2 In order to increase the acid strength of the generated acid, it is more ideal that all of them are fluorine atoms. 3 and Rf 4 Each independently represents a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. Among these, Rf 3 and Rf 4 It is preferred that at least one of the groups is a trifluoromethyl group.

[0658] In formula (B9), Rf 5 and Rf 6 Each independently represents a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms. 5 and Rf 6 At the same time, it is a hydrogen atom. Among these, in order to improve the solvent solubility, Rf 5 and Rf 6 It is preferred that at least one of the groups is a trifluoromethyl group.

[0659] In formulae (B9) and (B10), h is an integer of 0 to 3, and 1 is preferable.

[0660] Specific examples of the anion of the repeating unit B9 include those shown below, but are not limited to these. A Same as above.

[0661] [Chemistry 219]

[0662]

[0663] [Chemistry 220]

[0664]

[0665] [Chemistry 221]

[0666]

[0667] [Chemistry 222]

[0668]

[0669] [Chemistry 223]

[0670]

[0671] [Chemistry 224]

[0672]

[0673] [Chemistry 225]

[0674]

[0675] Specific examples of the anion of the repeating unit B10 include those shown below, but are not limited to these. A Same as above.

[0676] [Chemistry 226]

[0677]

[0678] [Chemistry 227]

[0679]

[0680] [Chemistry 228]

[0681]

[0682] [Chemistry 229]

[0683]

[0684] [Chemistry 230]

[0685]

[0686] [Chemistry 231]

[0687]

[0688] [Chemistry 232]

[0689]

[0690] Specific examples of the anion of the repeating unit B11 include those shown below, but are not limited to these. A Same as above.

[0691] [Chemistry 233]

[0692]

[0693] In formulas (B9) to (B11), A +Specific examples of the onium cation include: + The examples shown in the description are the same as those, but are not limited to these.

[0694] Among the repeating units B8 to B11, the units that are ideal for processing the blank photomask include the repeating units B9 and B10 in consideration of the best acid strength for the acid-labile groups of the designed polymer.

[0695] Repeating units B8 to B11 are units that generate acid due to irradiation with high-energy rays. It is believed that by including these units in the polymer, acid diffusion is moderately suppressed, and a pattern with reduced LER can be obtained. In addition, it is believed that by including these units in the polymer, the phenomenon of acid volatilization from the exposed part and re-attachment to the unexposed part during baking in a vacuum is suppressed, which is effective in reducing LER and reducing shape degradation caused by undesired film loss in the unexposed part.

[0696] Repeating units B8 to B11 are preferably introduced in the range of 0.1 to 30 mol %, more preferably in the range of 0.5 to 20 mol %, of all repeating units of the polymer contained in the base polymer. Repeating units B8 to B11 may be used alone or in combination of two or more.

[0697] The content of repeating units having an aromatic ring skeleton in all repeating units of the polymer contained in the above-mentioned base polymer is preferably 65 mol% or more, more preferably 75 mol% or more, and even more preferably 85 mol% or more. When repeating units B8 to B11 are not contained, it is more preferable that all units have an aromatic ring skeleton.

[0698] Among all the repeating units of the polymer contained in the above-mentioned base polymer, the content of repeating unit B1, repeating unit B2, repeating unit B3, repeating unit B4 and at least one selected from repeating units B5 to B7 is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more.

[0699] The polymer may also contain a commonly used (meth)acrylate unit protected by an acid-labile group or a (meth)acrylate unit having a lactone structure, a hydroxyl group other than a phenolic hydroxyl group, or other adhesion groups. These repeating units can be used to fine-tune the properties of the resist film, but these units may not be contained.

[0700] Examples of the (meth)acrylate unit having an adhesion group include a repeating unit represented by the following formula (B12) (hereinafter, also referred to as repeating unit B12), a repeating unit represented by the following formula (B13) (hereinafter, also referred to as repeating unit B13), and a repeating unit represented by the following formula (B14) (hereinafter, also referred to as repeating unit B14). These units do not exhibit acidity, but can be used auxiliaryly as units that provide adhesion to a substrate and units that adjust solubility.

[0701] [Chemistry 234]

[0702]

[0703] In formulas (B12) to (B14), R A Same as above. 41 is -O-, -S- or methylene. 42 is a hydrogen atom or a hydroxyl group. 43 It is a saturated hydrocarbon group having 1 to 4 carbon atoms. k is an integer of 0 to 3.

[0704] When repeating units B12 to B14 are included, their content is preferably 0 to 20 mol%, more preferably 0 to 10 mol% of all repeating units of the polymer contained in the base polymer. Repeating units B12 to B14 may be used alone or in combination of two or more.

[0705] The above-mentioned polymer can be synthesized by copolymerizing each monomer protected by a protecting group by a known method as needed, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited, and is preferably free radical polymerization or anionic polymerization. Regarding these methods, Japanese Patent Publication No. 2004-115630 can be used as a reference.

[0706] The weight average molecular weight (Mw) of the above-mentioned polymer is preferably 1000 to 50000, and more preferably 2000 to 20000. If Mw is 1000 or more, there will be no risk of the head of the pattern becoming rounded and the resolution being reduced, and at the same time, the LER degradation phenomenon will not occur as is known in the past. On the other hand, if Mw is 50000 or less, there will be no risk of LER degradation, especially when forming a pattern with a pattern line width of 100nm or less. In addition, in the present invention, Mw is a polystyrene-converted measurement value obtained by a gel permeation chromatograph (GPC) using tetrahydrofuran (THF) or dimethylformamide (DMF) as a solvent.

[0707] The molecular weight distribution (Mw / Mn) of the polymer is narrowly distributed in the range of 1.0 to 2.0, preferably 1.0 to 1.9, and more preferably 1.0 to 1.8. In the case of such a narrow distribution, no residues are generated on the pattern after development, and the shape of the pattern is not deteriorated.

[0708] In addition, with respect to the aforementioned base polymer design, the dissolution rate in the alkaline developer is preferably 10 nm / min or less, 7 nm / min or less, and 5 nm / min or less. In the advanced generation, when the coating film on the substrate is in the thin film region (100 nm or less), the effect of the pattern film loss by alkaline development becomes greater. When the alkaline dissolution rate of the polymer is greater than 10 nm / min, the pattern collapses and it becomes impossible to form a fine pattern. In particular, in the production of photomasks that require no defects, this is significant because there is a tendency for the development process to be strong. In addition, the dissolution rate of the base polymer in the present invention with respect to the alkaline developer is calculated by: spin coating a polymer solution (polymer concentration: 16.7 mass %, solvent: propylene glycol monomethyl ether acetate (PGMEA)) on an 8-inch silicon wafer, baking at 100°C for 90 seconds to form a film with a thickness of 1000 nm, and then developing with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 100 seconds, and the amount of film loss when the film is developed.

[0709] The aforementioned base polymer may contain, in addition to the base polymer containing the repeating unit B1, a base polymer having a known acid-labile group such as a tertiary alkyl group or a tert-butyloxycarbonyl group. In order to exert the effect of the present invention, it is preferred that the proportion of the base polymer containing the repeating unit B1 in all the base polymers contained in the resist composition is 30% or more.

[0710] The base polymer of the component (B) may contain other polymers other than the aforementioned polymers. As for other polymers, those conventionally known as base polymers for resist compositions can be used. The content of other polymers is not particularly limited unless the effects of the present invention are impaired.

[0711] [(C) Organic solvent]

[0712] The resist composition of the present invention may also contain an organic solvent as component (C). The organic solvent is not particularly limited as long as it can dissolve the components. Examples of such organic solvents include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone 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; and propylene glycol monomethyl ether (PGME). , ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; PGMEA, propylene glycol monoethyl ether acetate, ethyl lactate (EL), ethyl pyruvate, butyl acetate, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate and other esters; γ-butyrolactone and other lactones; their mixed solvents, etc. When using an acetal-based acid-labile group, in order to accelerate the deprotection reaction of the acetal, a high-boiling alcohol solvent may also be added, specifically diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol and the like.

[0713] Among these organic solvents, 1-ethoxy-2-propanol, PGMEA, PGME, cyclohexanone, EL, γ-butyrolactone, and mixed solvents thereof are particularly preferred.

[0714] When the chemically amplified positive resist composition of the present invention contains (C) an organic solvent, its content is preferably 200 to 10,000 parts by mass, more preferably 400 to 5,000 parts by mass, relative to 80 parts by mass of the base polymer (B). The organic solvent (C) may be used alone or in combination of two or more.

[0715] [(D) Fluorine-containing polymer]

[0716] The chemically amplified positive resist composition of the present invention may contain, as component (D), at least one selected from the group consisting of a repeating unit represented by the following formula (D1) (hereinafter, also referred to as repeating unit D1), a repeating unit represented by the following formula (D2) (hereinafter, also referred to as repeating unit D2), a repeating unit represented by the following formula (D3) (hereinafter, also referred to as repeating unit D3), and a repeating unit represented by the following formula (D4) (hereinafter, also referred to as repeating unit D4), and may further contain at least one selected from the group consisting of a repeating unit represented by the following formula (D5) (hereinafter, also referred to as repeating unit D5) and a repeating unit represented by the following formula (D6) (hereinafter, also referred to as repeating unit D6), and a fluorine atom-containing polymer for the purpose of achieving high contrast, suppressing chemical flare of acid during high-energy ray irradiation, shielding mixing of acid from the antistatic film in the process of coating the antistatic film material on the resist film, and suppressing unexpected and unnecessary pattern degradation. Since the aforementioned fluorine-atom-containing polymer also has the function of a surfactant, it can prevent the insoluble matter generated during the development process from re-adhering to the substrate, and thus can also play an effect of coping with development defects.

[0717] [Chemistry 235]

[0718]

[0719] In formulae (D1) to (D6), x is an integer of 1 to 3. y is an integer satisfying 0≤y≤5+2z-x. z is 0 or 1. w is an integer of 1 to 3. R B R is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. C Each is independently a hydrogen atom or a methyl group. 101 , R 102 , R 104 and R 105 Each R is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. 103 , R 106 , R 107 and R 108 are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-labile group, and in R 103 , R 106 , R 107 and R 108 When it is a hydrocarbon group or a fluorinated hydrocarbon group, the carbon-carbon bonds may be separated by ether bonds or carbonyl groups. 109 It is a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a hetero atom group interposed between carbon-carbon bonds. 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group between carbon-carbon bonds.111 W is a saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, and a portion of the -CH2- in the saturated hydrocarbon group may be substituted by an ester bond or an ether bond. 1 W is a (w+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (w+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms. 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-. 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-NH-W 31 -W 32 -.W 31 W is a single bond or a saturated alkylene group having 1 to 10 carbon atoms. 32 It is a single bond, ester bond, ether bond or sulfonamide bond. * indicates an atomic bond to a carbon atom of the main chain. )

[0720] In formula (D1) and (D2), R 101 , R 102 , R 104 and R 105 The saturated hydrocarbon group having 1 to 10 carbon atoms represented by ] may be straight-chain, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl; and cyclic saturated hydrocarbon groups having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl and norbornyl. Among these, saturated hydrocarbon groups having 1 to 6 carbon atoms are more preferred.

[0721] In formulas (D1) to (D4), R 103 , R 106 , R 107 and R 108 The hydrocarbon group having 1 to 15 carbon atoms represented by the above may be straight-chain, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 15 carbon atoms, alkenyl groups having 2 to 15 carbon atoms, alkynyl groups having 2 to 15 carbon atoms, etc., but alkyl groups having 1 to 15 carbon atoms are more preferred. As for the aforementioned alkyl groups, in addition to the aforementioned, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc. may be mentioned. In addition, as for the fluorinated hydrocarbon groups, examples include those in which a part or all of the hydrogen atoms bonded to the carbon atoms of the aforementioned hydrocarbon groups are substituted with fluorine atoms.

[0722] In formula (D4), W 1The (w+1)-valent hydrocarbon group having 1 to 20 carbon atoms represented by , for example, includes a group formed by removing w hydrogen atoms from an alkyl group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. 1 Examples of the (w+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by include groups in which at least one hydrogen atom in the aforementioned (w+1)-valent hydrocarbon group is substituted with a fluorine atom.

[0723] Specific examples of repeating units D1 to D4 include those shown below, but are not limited to these. B Same as above.

[0724] [Chemistry 236]

[0725]

[0726] [Chemistry 237]

[0727]

[0728] [Chemistry 238]

[0729]

[0730] In formula (D5), R 109 and R 110 As for the hydrocarbon group having 1 to 5 carbon atoms represented by , alkyl, alkenyl, alkynyl, etc. can be mentioned, but alkyl is more preferable. As for the aforementioned alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, etc. can be mentioned. In addition, between the carbon-carbon bonds of the aforementioned hydrocarbon groups, groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms can also be separated.

[0731] In formula (D5), -OR 109 It is more ideal to be a hydrophilic group. 109 For example, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms with an oxygen atom interposed between carbon-carbon bonds, or the like is preferred.

[0732] In formula (D5), W 2 It is preferably *-C(=O)-O- or *-C(=O)-NH-. Then, R C Methyl is more preferred. 2 The presence of carbonyl groups improves the ability of the antistatic film to capture acids. C If it is a methyl group, it will become a rigid polymer with a higher glass transition temperature (Tg), so the diffusion of acid will be suppressed. As a result, the stability of the resist film over time will be improved, and there will be no deterioration in resolution and pattern shape.

[0733] The repeating unit D5 may be exemplified by the following, but is not limited thereto. C Same as above.

[0734] [Chemistry 239]

[0735]

[0736] [Chemistry 240]

[0737]

[0738] In formula (D6), W 3 The saturated alkylene group having 1 to 10 carbon atoms may be straight-chain, branched or cyclic. Specific examples thereof include methanediyl, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, propane-2,2-diyl, butane-1,1-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-2,3-diyl, butane-1,4-diyl and 1,1-dimethylethane-1,2-diyl.

[0739] In formula (D6), R 111 The saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom may be straight-chain, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms or cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom.

[0740] The repeating unit D6 may be exemplified by the following, but is not limited thereto. C Same as above.

[0741] [Chemistry 241]

[0742]

[0743] [Chemistry 242]

[0744]

[0745] [Chemistry 243]

[0746]

[0747] [Chemistry 244]

[0748]

[0749] The content of repeating units D1 to D4 is preferably 15 to 95 mol %, more preferably 20 to 85 mol %, in all repeating units of the aforementioned fluorine-containing polymer. The content of repeating units D5 and / or D6 is preferably 5 to 85 mol %, more preferably 15 to 80 mol %, in all repeating units of the aforementioned fluorine-containing polymer. Repeating units D1 to D6 may be used alone or in combination of two or more.

[0750] (D) The fluorine-containing polymer may also contain other repeating units other than the aforementioned repeating units. Such repeating units include those described in paragraphs

[0046] to

[0078] of Japanese Patent Application Publication No. 2014-177407. When (D) the fluorine-containing polymer contains other repeating units, it is preferred that the content of the other repeating units is 50 mol% or less in all the repeating units of the aforementioned fluorine-containing polymer.

[0751] (D) The fluorine-containing polymer can be synthesized by copolymerizing monomers protected by protective groups as needed by a known method, and then performing a deprotection reaction as needed. The copolymerization reaction is not particularly limited, and is preferably free radical polymerization or anionic polymerization. For these methods, Japanese Patent Publication No. 2004-115630 can be used as a reference.

[0752] The Mw of the fluorine-containing polymer (D) is preferably 2000 to 50000, and more preferably 3000 to 20000. If the Mw is less than 2000, the diffusion of the acid may be promoted, the resolution may be deteriorated, and the stability over time may be impaired. If the Mw is too large, the solubility in the solvent may decrease, and coating defects may occur. In addition, the Mw / Mn of the fluorine-containing polymer (D) is preferably 1.0 to 2.2, and more preferably 1.0 to 1.7.

[0753] When the chemically amplified positive resist composition of the present invention contains (D) a fluorine-containing polymer, its content is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 80 parts by mass of the base polymer (B). The fluorine-containing polymer (D) may be used alone or in combination of two or more.

[0754] [(E) Quencher]

[0755] The chemically amplified positive resist composition of the present invention may contain a quencher as component (E) as necessary. In addition, the quencher in the present invention refers to a compound that captures the acid generated from the acid generator. This can suppress the diffusion rate of the acid generated from the acid generator when diffusing in the resist film, and even when a substrate composed of a material containing chromium on the outermost surface is used as the substrate, the influence of the acid generated in the resist film on the material containing chromium can be suppressed.

[0756] In the present invention, an example of a desirable quencher is a carboxylate onium salt represented by the following formula (E1).

[0757] [Chemistry 245]

[0758] R 201 -CO2 - Mq 十 (E1)

[0759] In formula (E1), R 201 It is a hydrocarbon group having 1 to 40 carbon atoms which may contain heteroatoms. The aforementioned hydrocarbon group may be saturated or unsaturated, and may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 40 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 40 carbon atoms, alkenyl groups having 2 to 40 carbon atoms, alkynyl groups having 2 to 40 carbon atoms, cyclic unsaturated aliphatic hydrocarbon groups having 3 to 40 carbon atoms, aryl groups having 6 to 40 carbon atoms, aralkyl groups having 7 to 40 carbon atoms, and groups obtained by combining these. In addition, part or all of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, an amide group, a nitro group, a thiol group, a sultone group, a sulfone group, or a group containing a sulfonium salt, and part of the -CH2- of the aforementioned hydrocarbon group may be substituted with an ether bond, an ester bond, a carbonyl group, a carbonate group, or a sulfonate bond.

[0760] In formula (E1), Mq + is an onium cation. Examples of the onium cation include sulfonium cations, iodonium cations, and ammonium cations, and sulfonium cations are more preferred. Preferred sulfonium cations include the same ones as those exemplified for the sulfonium cation represented by formula (cation-1).

[0761] When the chemically amplified positive resist composition of the present invention contains the carboxylate onium salt represented by formula (E1) as a quencher, its content is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 20 parts by mass, based on 80 parts by mass of the base polymer (B).

[0762] Other examples of the quencher include carboxylate onium salts represented by the following formula (E2) or (E3).

[0763] [Chemistry 246]

[0764]

[0765] In the formula, Mq + Same as above.

[0766] In formula (E2), R 211 ~R 214 are each independently a hydrogen atom, -L11 -CO2 - , or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 211 With R 212 , R 212 With R 213 , or R 213 With R 214 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded. 11 is a single bond or an alkylene group having 1 to 20 carbon atoms which may contain a hetero atom. 115 It is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom.

[0767] In formula (E2), ring R is a ring having 2 to 6 carbon atoms and a nitrogen atom in the formula, and some or all of the hydrogen atoms bonded to the carbon atoms in the ring may be replaced by a hydrocarbon group having 1 to 20 carbon atoms, or -L 11 -CO2 - The -CH2- of the ring may be substituted with a divalent group containing a sulfur atom, an oxygen atom or a nitrogen atom. The aforementioned ring may be an alicyclic ring or an aromatic ring. In addition, the aforementioned ring is preferably a 5-membered ring or a 6-membered ring. For specific examples thereof, pyridine ring, pyrrole ring, pyrrolidine ring, piperidine ring, pyrazole ring, imidazoline ring, pyridazine ring, pyrimidine ring, pyrazine ring, imidazoline ring, oxazole ring, thiazole ring, morpholine ring, thiazine ring, triazole ring, etc. may be cited.

[0768] The carboxylic acid onium salt represented by formula (E2) has at least one -L 11 -CO2 - That is, R 211 ~R 214 At least one of them is -L 11 -CO2 - , and / or at least one of the hydrogen atoms bonded to the carbon atoms of ring R is replaced by -L 11 -CO2 - replaced.

[0769] In formula (E3), R 221 ~R 226 Each R is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. 221 With R 222 , or R 223 With R 226 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded. 224 With R 225 They may also be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. k1 is 0 or 1. When k1=0, k2 is 0 or 1; when k1=1, k2 is an integer of 0-3.

[0770] When the chemically amplified positive resist composition of the present invention contains the carboxylate onium salt represented by formula (E2) or (E3) as a quencher, its content is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 80 parts by mass of the base polymer (B).

[0771] Other examples of the quencher include sulfonium compounds represented by the following formula (E4).

[0772] [Chemistry 247]

[0773]

[0774] In formula (E4), R 231 , R 232 and R 233 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom. In addition, a part of the hydrogen atoms of the aforementioned hydrocarbon group may be substituted by a group containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and a part of -CH2- of the aforementioned hydrocarbon group may be substituted by a group containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. As a result, a hydroxyl group, a cyano group, a carbonyl group, an ether bond, a thioether bond, an ester bond, a sulfonate bond, a carbonate bond, a carbamate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. may be contained. In addition, -CH2- of the aforementioned hydrocarbon group may be a carbon atom bonded to the benzene ring in the formula.

[0775] In formula (E4), z1 and z2 are each independently an integer of 0 to 5. z3 is an integer of 0 to 4. From the viewpoint of ease of synthesis and availability of raw materials, z1, z2 and z3 are each preferably 0, 1 or 2.

[0776] When z1 is 2 to 5, two adjacent R 231 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded. 232 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded. 233 They may also be bonded to each other to form a ring together with the carbon atoms to which they are bonded.

[0777] When the chemically amplified positive resist composition of the present invention contains the sulfonium compound represented by formula (E4) as a quencher, the content thereof is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, based on 80 parts by mass of the base polymer (B).

[0778] As for the quencher, in addition to the aforementioned onium salt compounds, a photodegradable onium salt having a nitrogen-containing substituent may be used as needed. This compound functions as a quencher in the unexposed part, and the exposed part loses the quencher ability by neutralization with the acid generated from itself, and functions as a so-called photodisintegration base. By using a photodisintegration base, the contrast between the exposed part and the unexposed part can be made stronger. As for the photodisintegration base, those described in Japanese Patent Publication No. 2009-109595, Japanese Patent Publication No. 2012-46501, Japanese Patent Publication No. 2013-209360, etc. can be cited. When the chemically amplified positive resist composition of the present invention contains the aforementioned photodisintegration base as a quencher, its content is preferably 0.1 to 40 parts by mass relative to 80 parts by mass of the base polymer (B), and more preferably 0.1 to 20 parts by mass.

[0779] As for the quencher, an amine compound can also be used. As for the aforementioned amine compound, examples include primary, secondary or tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103, and in particular, examples include amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, and a sulfonate bond. In addition, as in the compounds described in Patent Publication No. 3790649, examples include compounds in which primary or secondary amines are protected by carbamate groups. When the chemically amplified positive resist composition of the present invention contains the aforementioned amine compound as a quencher, its content is preferably 0.001 to 12 parts by mass relative to 80 parts by mass of the base polymer (B), and more preferably 0.01 to 8 parts by mass.

[0780] (E) The quencher may be used alone or in combination of two or more.

[0781] [(F) Other photoacid generators]

[0782] The chemically amplified positive resist composition of the present invention may also contain other photoacid generators other than the photoacid generator represented by formula (A). As for the aforementioned other photoacid generators, there is no particular limitation as long as they are compounds that generate acid due to high-energy radiation. As for ideal photoacid generators, there are sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate ion type photoacid generators, etc.

[0783] Specific examples of the other photoacid generators include nonafluorobutane sulfonate ions, partially fluorinated sulfonate ions described in paragraphs

[0247] to

[0251] of JP-A-2012-189977, partially fluorinated sulfonate ions described in paragraphs

[0261] to

[0265] of JP-A-2013-101271, paragraphs

[0122] to

[0142] of JP-A-2008-111103, and those described in paragraphs

[0080] to

[0081] of JP-A-2010-215608.

[0784] Preferred examples of the photoacid generator include salt compounds containing anions having the structures shown below.

[0785] [Chemistry 248]

[0786]

[0787] [Chemistry 249]

[0788]

[0789] [Chemistry 250]

[0790]

[0791] [Chemistry 251]

[0792]

[0793] [Chemistry 252]

[0794]

[0795] [Chemistry 253]

[0796]

[0797] [Chemistry 254]

[0798]

[0799] [Chemistry 255]

[0800]

[0801] [Chemistry 256]

[0802]

[0803] [Chemistry 257]

[0804]

[0805] Other preferred examples of the photo-acid generator include salt compounds containing an anion represented by the following formula (F1).

[0806] [Chemistry 258]

[0807]

[0808] In formula (F1), p is an integer of 1 to 3. q is an integer of 1 to 5. r is an integer of 0 to 3. s1 is 0 or 1.

[0809] In formula (F1), L 21 It is a single bond, an ether bond, an ester bond, a sulfonate bond, a carbonate bond or a carbamate bond.

[0810] In formula (F1), L 22 It is an ether bond, an ester bond, a sulfonate bond, a carbonate bond or a carbamate bond.

[0811] In formula (F1), L 23 When p is 1, it is a single bond or an alkylene group having 1 to 20 carbon atoms, and when p is 2 or 3, it is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and the alkylene group and the (p+1)-valent hydrocarbon group may 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 bond, a halogen atom, a hydroxyl group and a carboxyl group.

[0812] L 23 The alkylene group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkanediyl groups having 1 to 20 carbon atoms, such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; cyclic saturated alkylene groups having 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; unsaturated aliphatic alkylene groups having 2 to 20 carbon atoms, such as vinylene and propylene-1,3-diyl; arylene groups having 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining these. 23 The (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include groups obtained by removing one or two hydrogen atoms from the specific examples of the aforementioned hydrocarbon groups having 1 to 20 carbon atoms.

[0813] In formula (F1), Rf 1 and Rf 2Each is independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, and at least one is a fluorine atom or a trifluoromethyl group.

[0814] In formula (F1), R 301 is a hydroxyl group, a carboxyl group, a saturated hydrocarbon group having 1 to 6 carbon atoms, a saturated hydrocarbon oxy group having 1 to 6 carbon atoms, a saturated hydrocarbon carbonyloxy group having 2 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an amino group, -N(R 301A )-C(=O)-R 301B or -N(R 301A )-C(=O)-OR 301B , R 301A is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, R 301B It is a saturated hydrocarbon group having 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms.

[0815] R 301 , R 301A and R 301B The saturated hydrocarbon group having 1 to 6 carbon atoms represented by may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl; and cyclic saturated hydrocarbon groups having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. 301 The saturated hydrocarbon group of the saturated hydrocarbonoxy group having 1 to 6 carbon atoms represented by , may be the same as the specific examples of the saturated hydrocarbon group described above, and with respect to R 301 As for the saturated hydrocarbon group part of the saturated hydrocarbon carbonyloxy group having 2 to 6 carbon atoms represented by , those having 1 to 5 carbon atoms among the specific examples of the saturated hydrocarbon group having 1 to 6 carbon atoms described above can be mentioned.

[0816] R 301B The unsaturated aliphatic hydrocarbon group having 2 to 8 carbon atoms represented may be straight-chain, branched or cyclic. Specific examples thereof include alkenyl groups having 2 to 8 carbon atoms such as ethenyl, propenyl, butenyl and hexenyl; alkynyl groups having 2 to 8 carbon atoms such as ethynyl, propynyl and butynyl; and cyclic unsaturated aliphatic hydrocarbon groups having 3 to 8 carbon atoms such as cyclohexenyl and norbornenyl.

[0817] In formula (F1), R 302 It is a saturated alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 14 carbon atoms, and a part or all of the hydrogen atoms of the saturated alkylene group may be substituted by halogen atoms other than fluorine atoms, and a part or all of the hydrogen atoms of the arylene group may be substituted by a substituent selected from a saturated alkyl group having 1 to 20 carbon atoms, a saturated alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen atom and a hydroxyl group.

[0818] R 302The saturated alkylene group having 1 to 20 carbon atoms represented by the above-mentioned group may be straight-chain, branched or cyclic. Specific examples thereof include alkylene groups having 1 to 20 carbon atoms such as methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl and dodecane-1,12-diyl; and cyclic saturated alkylene groups having 3 to 20 carbon atoms such as cyclopentanediyl, cyclohexanediyl, norbornanediyl and adamantanediyl.

[0819] Just R 302 Specific examples of the arylene group having 6 to 14 carbon atoms include phenylene, naphthylene, phenanthrene-diyl, anthracene-diyl, etc. The hydrocarbon radical of the saturated hydrocarbon group having 1 to 20 carbon atoms and the hydrocarbonoxy group having 1 to 20 carbon atoms as a substituent of the arylene group may be straight-chain, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.; and cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Specific examples of the arylene group having 6 to 14 carbon atoms as the substituent of the arylene group include phenylene, naphthylene, phenanthrenediyl, anthracenediyl and the like.

[0820] The anion represented by the formula (F1) is preferably an anion represented by the following formula (F2).

[0821] [Chemistry 259]

[0822]

[0823] In formula (F2), p, q, r, L 21 , L 23 and R 301 Same as above. s2 is an integer from 1 to 4. 302A is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbonoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen atom or a hydroxyl group. 302A They can be the same or different.

[0824] Examples of the anion represented by formula (F1) include the following, but are not limited to these.

[0825] [Chemistry 260]

[0826]

[0827] [Chemistry 261]

[0828]

[0829] [Chemistry 262]

[0830]

[0831] [Chemistry 263]

[0832]

[0833] [Chemistry 264]

[0834]

[0835] [Chemistry 265]

[0836]

[0837] [Chemistry 266]

[0838]

[0839] [Chemistry 267]

[0840]

[0841] [Chemistry 268]

[0842]

[0843] [Chemistry 269]

[0844]

[0845] [Chemistry 270]

[0846]

[0847] [Chemistry 271]

[0848]

[0849] [Chemistry 272]

[0850]

[0851] [Chemistry 273]

[0852]

[0853] [Chemistry 274]

[0854]

[0855] [Chemistry 275]

[0856]

[0857] [Chemistry 276]

[0858]

[0859] [Chemistry 277]

[0860]

[0861] [Chemistry 278]

[0862]

[0863] [Chemistry 279]

[0864]

[0865] [Chemistry 280]

[0866]

[0867] [Chemistry 281]

[0868]

[0869] [Chemistry 282]

[0870]

[0871] [Chemistry 283]

[0872]

[0873] [Chemistry 284]

[0874]

[0875] [Chemistry 285]

[0876]

[0877] [Chemistry 286]

[0878]

[0879] [Chemistry 287]

[0880]

[0881] In (F) other photoacid generators, the cations that form a pair with the anions are preferably sulfonium cations or iodonium cations. Specific examples of the sulfonium cations include, but are not limited to, the same sulfonium cations as those exemplified for the sulfonium cations represented by formula (cation-1). Specific examples of the iodonium cations include, but are not limited to, the same sulfonium cations as those exemplified for the sulfonium cations represented by formula (cation-2).

[0882] The acid generated by the aforementioned other photoacid generator preferably has a pKa of -2.0 or more, and more preferably -1.0 or more. The upper limit of the pKa is preferably 2.0. The pKa value is calculated using pKa DB in ACD / Chemsketch ver: 9.04, a software produced by Advanced Chemistry Development, Inc.

[0883] When the chemically amplified positive resist composition of the present invention contains (F) other photoacid generators, the content thereof is preferably 1 to 10 parts by mass, and more preferably 1 to 5 parts by mass, relative to 80 parts by mass of the base polymer. (F) Other photoacid generators may be used alone or in combination of two or more. By including other photoacid generators, the amount of acid generated in the exposed portion and the dissolution inhibition performance of the unexposed portion can be appropriately adjusted.

[0884] [(G) Surfactant]

[0885] The chemically amplified positive resist composition of the present invention may also contain a conventional surfactant as component (G) in order to improve the coating properties on the substrate. The aforementioned surfactant is generally known in the art as described in International Publication No. 2006 / 121096, Japanese Patent Publication No. 2008-102383, Japanese Patent Publication No. 2008-304590, Japanese Patent Publication No. 2004-115630, and Japanese Patent Publication No. 2005-8766, and may be selected as a reference.

[0886] When the chemically amplified positive resist composition of the present invention contains (G) a surfactant, its content is preferably 2 parts by mass or less, more preferably 1 part by mass or less, based on 80 parts by mass of the (B) base polymer, and its lower limit is preferably set to 0.01 parts by mass or more.

[0887] [Resist pattern forming method]

[0888] The resist pattern forming method of the present invention comprises the following steps: forming a resist film on a substrate using the aforementioned chemically amplified positive resist composition; irradiating a pattern on the aforementioned resist film using high-energy rays (i.e., exposing the aforementioned resist film using high-energy rays); and developing the resist film after the aforementioned irradiation pattern using an alkaline developer.

[0889] As for the aforementioned substrate, for example, a substrate for integrated circuit manufacturing (Si, SiO, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.), or a substrate for transmissive or reflective mask circuit manufacturing (Cr, CrO, CrON, MoSi2, Si, SiO, SiO2, SiON, SiONC, CoTa, NiTa, TaBN, SnO2, etc.) can be used. The aforementioned chemically amplified positive resist composition is applied to the aforementioned substrate by a method such as spin coating so that the film thickness becomes 0.03 to 2 μm, and is pre-baked on a hot plate at a temperature of preferably 60 to 150° C. for 1 to 20 minutes, more preferably 80 to 140° C. for 1 to 10 minutes, to form a resist film.

[0890] Then, the resist film is exposed to light using high-energy rays to irradiate the pattern. Examples of the high-energy rays include ultraviolet rays, far ultraviolet rays, excimer lasers (KrF, ArF, etc.), EUV, X-rays, gamma rays, synchrotron radiation, and EB. In the present invention, it is preferred to use EUV or EB for exposure.

[0891] When ultraviolet rays, extreme ultraviolet rays, excimer lasers, EUV, X-rays, gamma rays or synchrotron radiation are used as the high-energy radiation, a mask for forming a target pattern is used so that the exposure dose is preferably 1 to 500 mJ / cm 2 , more preferably 10 to 400 mJ / cm 2 When EB is used, the exposure dose is preferably 1 to 500 μC / cm in order to form the target pattern. 2 , more preferably 10 to 400 μC / cm 2 way of irradiation.

[0892] For exposure, in addition to the usual exposure method, an immersion method in which the space between the mask and the resist film is wetted may be used depending on the situation. In this case, a protective film insoluble in water may be used.

[0893] Then, a post-exposure bake (PEB) is performed on a hot plate at preferably 60 to 150° C. for 1 to 20 minutes, more preferably 80 to 140° C. for 1 to 10 minutes.

[0894] Afterwards, using a developer containing an alkaline aqueous solution of TMAH such as 0.1 to 5% by mass, preferably 2 to 3% by mass, development is performed by general methods such as dipping, puddle, and spraying under conditions of preferably 0.1 to 3 minutes, more preferably 0.5 to 2 minutes, to form a target pattern on the substrate.

[0895] In addition, the chemically amplified positive resist composition of the present invention is particularly useful in forming patterns with good resolution and low LER. Furthermore, since it is difficult to obtain the adhesion of the resist pattern, the chemically amplified positive resist composition of the present invention is particularly useful in forming patterns on substrates whose surfaces have materials that are prone to pattern peeling and pattern collapse. Examples of such substrates include substrates on which metallic chromium or a chromium compound containing one or more light elements selected from oxygen, nitrogen, and carbon is sputtered to form a film on the outermost surface; substrates containing SiO, SiO x , tantalum compounds, molybdenum compounds, cobalt compounds, nickel compounds, tungsten compounds, tin compounds, etc. The chemically amplified positive resist composition of the present invention is particularly useful in pattern formation using a blank photomask as a substrate. In this case, the blank photomask may be a transmissive type or a reflective type.

[0896] As for the transmission type blank photomask, the blank photomask having a light shielding film made of a chromium-based material may be a blank photomask for a binary mask or a blank photomask for a phase shift mask. In the case of a blank photomask for a binary mask, it may be a blank photomask having an anti-reflection layer and a light shielding layer made of a chromium-based material as the light shielding film; or it may be a blank photomask in which the entire anti-reflection film on the surface side or only the further surface side of the anti-reflection film on the surface side is a chromium-based material, and the remaining part is, for example, composed of a silicon-based compound material that may also contain a transition metal. In addition, in the case of a blank photomask for a phase shift mask, a blank photomask for a phase shift mask having a chromium-based light shielding film on the phase shift film may be used as an object.

[0897] The aforementioned blank photomask having a chromium-based material on the outermost layer is very well known, as exemplified in Japanese Patent Publication No. 2008-26500, Japanese Patent Publication No. 2007-302873 or any of them as the current technology, and a detailed description is omitted, but for example, when a shading film having an anti-reflection layer and a shading layer is formed by using a chromium-based material, a film structure as described below can be used.

[0898] When a light-shielding film having an anti-reflection layer and a light-shielding layer is formed by using a chromium-based material, the anti-reflection layer and the light-shielding layer may be laminated in the order of the surface layer side, or in the order of the anti-reflection layer, the light-shielding layer, and the anti-reflection layer. In addition, the anti-reflection layer and the light-shielding layer may each be a plurality of layers, and the composition of the layers having different compositions may be discontinuously changed or continuously changed. As for the chromium-based material used, metallic chromium and materials containing light elements such as oxygen, nitrogen, and carbon in metallic chromium may be used. Specifically, metallic chromium, chromium oxide, chromium nitride, chromium carbide, chromium nitride oxide, chromium carbide oxide, chromium carbide nitride, chromium carbide oxide, chromium carbide nitride, chromium carbide nitride, chromium carbide nitride, chromium carbide nitride, and chromium carbide nitride.

[0899] A reflective blank mask is provided, which comprises: a substrate; a multilayer reflective film formed on one of the main surfaces (outer surface) of the substrate, specifically, a multilayer reflective film that reflects exposure light such as EUV light; and an absorber film formed on the multilayer reflective film, specifically, an absorber film that absorbs exposure light such as EUV light and reduces reflectivity. A reflective mask (reflective mask for EUV) having an absorber pattern (absorber film pattern) formed by patterning the absorber film is manufactured from the reflective blank mask (reflective blank mask for EUV). The wavelength of EUV light used in EUV lithography is 13 to 14 nm, and is usually light with a wavelength of about 13.5 nm.

[0900] The multilayer reflective film is usually preferably disposed adjacent to one of the main surfaces of the substrate, but a base film may be disposed between the substrate and the multilayer reflective film if the effect of the present invention is not impaired. The absorber film may also be formed adjacent to the multilayer reflective film, but a protective film (a protective film of the multilayer reflective film) may be disposed between the multilayer reflective film and the absorber film, preferably adjacent to the multilayer reflective film, or more preferably adjacent to the multilayer reflective film and the absorber film. The protective film is used to protect the multilayer reflective film during processing such as cleaning and correction. Furthermore, the protective film is preferably one that has the function of protecting the multilayer reflective film when patterning is performed by etching the absorber film and preventing oxidation of the multilayer reflective film. On the other hand, under the other main surface (inner surface) on the opposite side of one of the main surfaces of the substrate, a conductive film for electrostatically adsorbing the reflective mask to the exposure device may also be disposed adjacent to the other main surface, preferably. In addition, although one of the main surfaces of the substrate is defined as the outer surface and the upper side, and the other main surface is defined as the inner surface and the lower side, the outer and inner sides and the upper and lower sides of the two are determined for convenience. The so-called one of the main surfaces and the other main surface are any of the two main surfaces (film forming surfaces) in the substrate, and the outer and inner sides and the upper and lower sides are interchangeable. More specifically, it can be formed by a method such as that exemplified in Japanese Patent Publication No. 2021-139970 or therein as the current technology.

[0901] By means of the resist pattern forming method of the present invention, even when using a substrate (such as a transmissive or reflective blank mask) whose outermost surface is made of a material that is easily affected by the shape of the resist pattern, such as chromium, silicon or tantalum, a pattern with high resolution and small dimensional difference that is independent of the density of the pattern and in which the influence of the development load and development residue defects are suppressed can be obtained.

[0902] Example

[0903] Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. The following apparatuses were used.

[0904] IR: NICOLET 6700 manufactured by Thermo Fisher Scientific

[0905] · 1 H-NMR: ECA-500 manufactured by JEOL Ltd.

[0906] ·MALDI TOF-MS: S3000 manufactured by JEOL Ltd.

[0907] [1] Synthesis of photoacid generator

[0908] [Example 1-1] Synthesis of Photoacid Generator PAG-1

[0909] [Chemistry 288]

[0910]

[0911] Under a nitrogen environment, SM-2 (8.5 g) was suspended in a mixed solvent of THF (40 g) and water (40 g). After adding a 25% by mass sodium hydroxide aqueous solution (3.3 g) dropwise thereto, the mixture was stirred at room temperature for 2 hours to dissolve SM-2. Thereafter, SM-1 (8.5 g) was directly added in the form of a powder and aged at room temperature for 10 hours. After maturation, the reaction solution was cooled and water (80 g) was added to stop the reaction. The target product was extracted with dichloromethane (160 g), and a conventional aqueous work-up was performed. After the solvent was distilled off, it was recrystallized with diisopropyl ether to obtain 16.9 g of the photoacid generator PAG-1 (yield 86%).

[0912] The IR spectrum data and TOF-MS results of PAG-1 are shown below. 1 The results of H-NMR / DMSO-d6 are shown in Figure 1 middle.

[0913] IR(D-ATR):ν=3070,2973,2927,2853,1634,1598,1561,1483,1468,1446,1390,1378,1365,1356,1327,1272,1260,1237,1225, 1189,1166,1129,1111,1073,1050,1008,999,981,889,864,842,815,777,768,758,748,736,682,630,580,562,534,501,485cm -1 .

[0914] MALDI TOF-MS:POSITIVE M + 277 (equivalent to C 18 H 13 OS + )

[0915] NEGATIVE M - 631 (equivalent to C 30 H 35 F4O6S2 - )

[0916] [Examples 1-2 to 1-7] Synthesis of PAG-2 to PAG-7

[0917] Photoacid generators PAG-2 to PAG-7 represented by the following formulae were synthesized using corresponding raw materials and known organic synthesis reactions.

[0918] [Chemistry 289]

[0919]

[0920] [2]Synthesis of monomers

[0921] [Synthesis Example 2-1] Synthesis of Monomer a1-1

[0922] [Chemistry 290]

[0923]

[0924] (1) Synthesis of intermediate Pre-a1-1

[0925] Under nitrogen atmosphere, sodium hydride (purity 55% by mass, 144.0 g) was suspended in THF (800 mL), and a solution consisting of 1-isopropylcyclopentanol (465.4 g) and THF (380 mL) was added dropwise. After the addition, the mixture was heated under reflux for 4 hours to prepare a metal alkoxide. Thereafter, raw material M-1 (854.7 g) was added dropwise, and the mixture was heated under reflux and matured for 18 hours. The reaction solution was cooled in an ice bath, and the reaction was stopped with water (1200 mL). The target product was extracted with a solvent consisting of toluene (1000 mL) and hexane (1000 mL), and a conventional aqueous work-up was performed. After the solvent was distilled off, the mixture was purified by distillation to obtain 816.2 g of the intermediate Pre-a1-1 (yield 67%) as a colorless oil.

[0926] (2) Synthesis of Monomer a1-1

[0927] Under nitrogen atmosphere, a Grignard reagent was prepared from magnesium (56.7 g), THF (900 g) and the intermediate Pre-a1-1 (816.2 g). The mixture was diluted with toluene (450 g) and the reaction system was cooled to below 10°C. Subsequently, [1,3-bis(diphenylphosphino)propane]nickel(II) dichloride (6.0 g) was added and stirred for 30 minutes at a temperature of below 10°C. After stirring, a solution consisting of vinyl bromide (260.3 g), THF (450 g) and toluene (450 g) was added dropwise while maintaining the temperature of the reaction system at below 20°C. After the addition was terminated, the reaction system was aged for 1 hour at a temperature of below 20°C. After the aging, the reaction system was cooled and an aqueous solution consisting of ammonium chloride (233 g), 20% by mass hydrochloric acid (233 g) and water (1165 g) was added dropwise to stop the reaction. Thereafter, the target product was extracted with hexane (2000 g), subjected to a conventional aqueous work-up, and after the solvent was distilled off, it was purified by distillation to obtain 519.5 g of the monomer a1-1 as a colorless oil (yield 74%).

[0928] The IR spectrum data and NMR spectrum of monomer a1-1 ( 1 The results of H-NMR / DMSO-d6) are shown below.

[0929] IR(D-ATR):ν=2966,2877,1597,1584,1504,1470,1454,1417,1391,1369,135 2,1253,1225,1201,1167,1122,1033,984,911,868,831,800,752,699,627cm -1 .

[0930] 1 H-NMR(600MHz in DMSO-d6): δ=7.27(1H,d),7.18(1H,d),7.13(1H,d),6.74(1H,dd),5.80(1 H,d),5.29(1H,d),2.47(2H,m),1.87(4H,m),1.54(4H,m),0.90(6H,d)ppm.

[0931] [Synthesis Examples 2-2 to 2-7] Synthesis of Monomers a1-2 to a1-7

[0932] The monomers a1-2 to a1-7 shown below were synthesized by using corresponding raw materials and various organic synthesis reactions.

[0933] [Chemistry 291]

[0934]

[0935] [3] Synthesis of base polymer

[0936] The structure of the repeating unit introduced into the polymer is shown below.

[0937] [Chemistry 292]

[0938]

[0939] [Chemistry 293]

[0940]

[0941] [Chemistry 294]

[0942]

[0943] [Chemistry 295]

[0944]

[0945] [Chemistry 296]

[0946]

[0947] [Chemistry 297]

[0948]

[0949] [Synthesis Example 3-1] Synthesis of polymer P-1

[0950] Under a nitrogen atmosphere, 52.9 g of 4-acetoxystyrene, 39.4 g of monomer a1-1, 7.6 g of acenaphthene, 7.4 g of dimethyl-2,2'-azobis-(2-methylpropionate) (manufactured by Fuji Film & Wako Pure Chemical Industries, Ltd., trade name V601) and 139 g of methyl ethyl ketone as a solvent were added to a 300 mL dropping tube to prepare a solution.

[0951] Then, in another 500mL polymerization flask set in a nitrogen environment, 62g of methyl ethyl ketone was added, and the above solution was added dropwise over 4 hours while being heated to 80°C. After the addition was terminated, the polymerization temperature was maintained at 80°C while stirring was continued for 18 hours, and then cooled to room temperature. The obtained polymerization solution was added dropwise to 1000g of hexane, and the precipitated copolymer was filtered. The filtered copolymer was washed twice with 500g of hexane. The obtained copolymer was dissolved in a mixed solvent of 150g of tetrahydrofuran and 50g of methanol in a 1L flask under a nitrogen environment, 22.3g of ethanolamine was added, and stirred at 60°C for 3 hours. The reaction solution was concentrated under reduced pressure, and the obtained concentrate was dissolved in a mixed solvent of 240g of ethyl acetate and 60g of water. The obtained solution was transferred to a separatory funnel, 11.1g of acetic acid was added, and a separation operation was performed. The lower layer was removed, and 60 g of water and 14.8 g of pyridine were added to the obtained organic layer to perform a liquid separation operation. The lower layer was removed, and 60 g of water was added to the obtained organic layer to perform water washing and liquid separation (water washing and liquid separation were performed 5 times in total). After the organic layer after liquid separation was concentrated, it was dissolved in 130 g of acetone, and the obtained acetone solution was added dropwise to 1200 g of water. The obtained crystalline precipitate was filtered, washed with water, and suction filtered for 2 hours. The obtained filtrate was dissolved in 130 g of acetone again, and the obtained acetone solution was added dropwise to 1200 g of water. The obtained precipitate was filtered, washed with water and dried to obtain 56.3 g of the target polymer P-1 which is a white polymer. Polymer P-1 was prepared by 13 C-NMR, 1 H-NMR and GPC measurements were performed to obtain the following analysis results.

[0952] [Chemistry 298]

[0953]

[0954] [Synthesis Examples 3-2 to 3-30, Comparative Synthesis Examples 1-1 to 1-15] Synthesis of Polymers P-2 to P-30, Comparative Polymers CP-1 to CP-15

[0955] The following polymers P-2 to P-30 were synthesized with reference to Synthesis Example 3-1 and a known method except that the types and blending ratios of the monomers were changed.

[0956] [Table 1]

[0957]

[0958]

[0959] [Table 2]

[0960]

[0961] [Table 3]

[0962]

[0963]

[0964] [4] Preparation of chemically amplified positive resist composition

[0965] [Examples 1-1 to 1-50, Comparative Examples 1-1 to 1-32]

[0966] The chemically amplified positive resist composition was prepared by dissolving the components shown in Tables 4 to 7 below in an organic solvent, and filtering the obtained solution through a 5 nm nylon filter and a 1 nm UPE filter. In addition, the aforementioned organic solvent was a mixed solvent of 940 parts by mass of PGMEA, 1870 parts by mass of EL, and 1870 parts by mass of PGME.

[0967] [Table 4]

[0968]

[0969]

[0970] [Table 5]

[0971]

[0972]

[0973] [Table 6]

[0974]

[0975]

[0976] [Table 7]

[0977]

[0978] In addition, in Tables 4 to 7, the structures of the comparative photoacid generators cPAG-1 to cPAG-4, photoacid generators PAG-A and PAG-B, quenchers Q-1 to Q-4, and fluorine-containing polymers FP-1 to FP-5 are as follows.

[0979] [Chemistry 299]

[0980]

[0981] [Chemistry 300]

[0982]

[0983] [Chemistry 301]

[0984]

[0985] [Chemistry 302]

[0986]

[0987] [4]EB Lithography Evaluation

[0988] [Examples 2-1 to 2-50, Comparative Examples 2-1 to 2-32]

[0989] Each chemically amplified positive resist composition (R-1 to R-50, CR-1 to CR-32) was spin-coated using ACT-M (manufactured by Tokyo Electron Co., Ltd.) on a blank mask as a reflective blank for EUV exposure mask, which was a 6-inch low thermal expansion glass substrate on which a 284nm thick Mo / Si40-layer multilayer reflective film was formed, a 3.5nm thick Ru film was formed as a protective film, a 70nm thick TaN film was formed as an absorption layer, and a 6nm thick CrN film was formed as a hard mask, and pre-baked on a hot plate at 110°C for 600 seconds to prepare a resist film with a film thickness of 80nm. The film thickness of the obtained resist film was measured using an optical measuring instrument NanoSpec (manufactured by Nanometrics Co., Ltd.). The measurement was performed at 81 locations in the surface of the blank substrate by removing the outer edge portion 10 mm inward from the outer periphery, and the average film thickness and the film thickness range were calculated.

[0990] The resist film was then exposed using an electron beam exposure apparatus (EBM-5000plus manufactured by NuFlare Technology, accelerating voltage 50 kV), subjected to PEB at 110° C. for 600 seconds, and developed with a 2.38 mass % TMAH aqueous solution to obtain a positive pattern.

[0991] The obtained resist pattern was evaluated as follows. The produced blank mask with pattern was observed by an aerial SEM (scanning electron microscope), and the exposure amount that allowed a 1:1 resolution of a 200nm straight line and space pattern (LS) was defined as the optimum exposure amount (μC / cm 2), and the minimum size in the exposure amount that can resolve an isolated interval of 200nm at a ratio of 9:1 is defined as the resolution (limit IS resolution), and the LER of 200nmLS is measured by SEM. For the evaluation of development load, the exposure amount (μC / cm2) that can resolve a 1:1LS designed for 200nm at a ratio of 1:1 is measured by SEM in the substrate surface. 2 ) and the spacing size of the 200nmLS pattern with dummy patterns of 15%, 25%, 33%, 45%, 50%, 55%, 66%, 75%, 85%, and 95% respectively arranged around the pattern, and the difference in the size of the sparse and dense patterns was compared. The pattern shape was visually determined to be rectangular.

[0992] The exposure dissolution rate is calculated by spin coating the resist solution on an 8-inch silicon wafer, baking it at 110°C for 60 seconds to form a 90nm thick resist film, and then applying a 1:1 line and space pattern (LS) of 200nm to the wafer at an exposure dose (mJ / cm 2 ) was calculated by exposing with a KrF excimer laser, baking at 110°C for 60 seconds, and developing with a 2.38 mass % TMAH aqueous solution at 23°C using a resist development analyzer (RDA-800 manufactured by Litho Tech Japan Co., Ltd.). The results are shown in Tables 8 to 10.

[0993] [Table 8]

[0994]

[0995] [Table 9]

[0996]

[0997]

[0998] [Table 10]

[0999]

[1000]

[1001] The results shown in Tables 8 to 10 indicate that the chemically amplified positive resist composition and resist pattern forming method of the present invention are useful in semiconductor device manufacturing, especially in optical lithography in the processing of transmission type and reflection type blank photomasks.

Claims

1. A chemically amplified positive resist composition comprising: (A) a photoacid generator represented by the following formula (A) which generates an acid due to the action of high-energy rays; and (B) a base polymer comprising a polymer having a repeating unit represented by the following formula (B1) whose solubility in an aqueous alkali solution is increased by the action of an acid; wherein n1 and n2 are each independently an integer of 0 to 2; n3 is an integer of 1≤n3≤4 when n2=0, an integer of 1≤n3≤6 when n2=1, and an integer of 1≤n3≤8 when n2=2; n4 is an integer of 0≤n4≤3 when n2=0, an integer of 0≤n4≤5 when n2=1, and an integer of 0≤n4≤7 when n2=2; but n3+n4 is 1≤n3+n4≤4 when n2=0, 1≤n3+n4≤6 when n2=1, and 1≤n3+n4≤8 when n2=2; n5 is an integer of 1≤n5≤5 when n1=0, an integer of 1≤n5≤7 when n1=1, and an integer of 1≤n5≤9 when n1=2; R 1 is an iodine atom, or a branched or cyclic hydrocarbon group having 3 to 20 carbon atoms which may contain a hetero atom, and at least one R 1 and L A The carbon atoms to which the carbon atom is bonded are bonded to adjacent carbon atoms; and when n5 is 2 or more, multiple R 1 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded; R 2 is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, and when n4 is 2 or more, a plurality of R 2 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded; R F1 is a fluorine atom, a fluorinated alkyl group having 1 to 6 carbon atoms, a fluorinated alkoxy group having 1 to 6 carbon atoms, or a fluorinated thioalkoxy group having 1 to 6 carbon atoms; L A and L B each independently a single bond, an ether bond, an ester bond, an amide bond, a sulfonate bond, a carbonate bond or a carbamate bond; X L is a single bond or an alkylene group having 1 to 40 carbon atoms which may contain a hetero atom; Z + is an onium cation; In the formula, a1 is an integer of 0 to 2; a2 is an integer of 1 or 2; a3 is an integer of 1 or 2; a4 is an integer of 0 to 4; R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; X 1 is a single bond or *-C(=O)-O-; * represents an atomic bond to a carbon atom of the main chain; R AL It is an acid-labile group; R F2 is a fluorine atom, a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms, a fluorinated saturated hydrocarbon oxy group having 1 to 6 carbon atoms, or a fluorinated saturated hydrocarbon thio group having 1 to 6 carbon atoms; R 11 is a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; Again, when a2 = 1, -OR AL and-R F2 must be bonded to adjacent carbon atoms on the aromatic ring; then, when a2 = 2, the two -OR AL One of them must be bonded to -R F2 The carbon atom adjacent to the carbon atom on the aromatic ring to which it is bonded.

2. The chemically amplified positive resist composition according to claim 1, in, The photoacid generator is represented by the following formula (A1); In the formula, n1~n5, R 1 , R 2 , R F1 , L A , X L and Z + Same as above.

3. The chemically amplified positive resist composition according to claim 1, in, Z + It is a sulfonium cation represented by the following formula (cation-1) or an iodonium cation represented by the following formula (cation-2); In the formula, R ct1 ~R ct5 are each independently a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may contain a hetero atom; and R ct1 and R ct2 They may also bond to each other to form a ring together with the sulfur atom to which they are bonded.

4. The chemically amplified positive resist composition according to claim 1, in, R AL A group represented by the following formula (AL-1) or (AL-2); In the formula, R L1 , R L2 and R L3 are each independently a hydrocarbon group having 1 to 12 carbon atoms, and the -CH 2 - may be partially substituted by -O- or -S-; when the hydrocarbon group contains an aromatic ring, part or all of the hydrogen atoms of the aromatic ring may be substituted by a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms which may also contain a halogen atom, or an alkoxy group having 1 to 4 carbon atoms which may also contain a halogen atom; and, R L1 and R L2 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded; R L4 and R L5 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R L6 is a hydrocarbon group having 1 to 20 carbon atoms, wherein -CH 2 - may also be substituted by -O- or -S-; and, R L5 and R L6 They can also bond to each other and to the carbon atoms and X 2 Together they form a heterocyclic group having 3 to 20 carbon atoms, wherein -CH 2 Part of - may also be replaced by -O- or -S-; X 2 is -O- or -S-; m1 and m2 are each independently 0 or 1; * indicates a bond to an adjacent -O- atom.

5. The chemically amplified positive resist composition according to claim 1, in, The polymer further comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B2) and a repeating unit represented by the following formula (B3); In the formula, b1 is 0 or 1; b2 is an integer from 0 to 2; b3 is an integer satisfying 0≤b3≤5+2(b2)-b4; b4 is an integer from 1 to 3; b5 is 0 or 1; c1 is an integer from 0 to 2; c2 is an integer from 0 to 2; c3 is an integer from 0 to 5; c4 is an integer from 0 to 2; R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; A 1 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, wherein -CH 2 Part of - can also be replaced by -O-; A 2 is a single bond, phenylene, naphthylene or *-C(=O)-OA 21 -;A 21 It is an aliphatic alkylene group having 1 to 20 carbon atoms which may contain a hydroxyl group, an ether bond, an ester bond or a lactone ring, or a phenylene group or a naphthylene group; * represents an atomic bond to a carbon atom of the main chain; R 12 is a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarboncarbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom; R 13 and R 14 are each independently a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and R 13 and R 14 They may also bond to each other and form a ring together with the carbon atoms to which they are bonded; R 15 Each is independently a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, or a fluorinated alkoxy group having 1 to 5 carbon atoms; R 16 Each is independently a hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom; X is an acid-labile group when b4 is 1, and is a hydrogen atom or an acid-labile group when b4 is 2 or 3, but at least one of them is an acid-labile group.

6. The chemically amplified positive resist composition according to claim 1, in, The polymer further comprises a repeating unit represented by the following formula (B4); Wherein, d1 is an integer satisfying 0≤d1≤5+2(d3)-d2; d2 is an integer from 1 to 3; d3 is an integer from 0 to 2; R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; Y 1 is a single bond, *-C(=O)-O- or *-C(=O)-NH-; * represents an atomic bond to a carbon atom of the main chain; A 3 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, wherein -CH 2 Part of - can also be replaced by -O-; R 21 It is a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 6 carbon atoms which may be substituted by a halogen atom.

7. The chemically amplified positive resist composition according to claim 1, in, The polymer comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B5), a repeating unit represented by the following formula (B6), and a repeating unit represented by the following formula (B7); In the formula, e is an integer of 0 to 6; f is an integer of 0 to 4; g1 is 0 or 1; g2 is an integer of 0 to 2; g3 is an integer of 0 to 5; R A is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 22 and R 23 Each is independently a hydroxyl group, a halogen atom, a saturated hydrocarbon carbonyloxy group having 2 to 8 carbon atoms which may be substituted by a halogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a halogen atom, or a saturated hydrocarbonoxy group having 1 to 8 carbon atoms which may be substituted by a halogen atom; R 24 is a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbonoxy group having 1 to 20 carbon atoms, a saturated hydrocarboncarbonyloxy group having 2 to 20 carbon atoms, a saturated hydrocarbonoxyalkyl group having 2 to 20 carbon atoms, a saturated hydrocarbonthioalkyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group or a cyano group, and when g2 is 1 or 2, it may also be a hydroxyl group; A 4 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms, wherein -CH 2 A part of - may be substituted by -O-.

8. The chemically amplified positive resist composition according to claim 1, in, The polymer further comprises at least one selected from the group consisting of a repeating unit represented by the following formula (B8), a repeating unit represented by the following formula (B9), a repeating unit represented by the following formula (B10), and a repeating unit represented by the following formula (B11); In the formula, R A are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; Z 1 is a single bond or a phenylene group; Z 2 for* 1 -C(=O)-OZ 21 -, * 1 -C(=O)-NH-Z 21 -or* 1 -OZ 21 -;Z 21 An aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, or a divalent group obtained by combining them, and may also contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group;* 1 Represents Z 1 Atomic bonds; Z 3 Each independently represents a single bond, phenylene, naphthylene or * 2 -C(=O)-OZ 31 -;Z 31 is an aliphatic alkylene group having 1 to 10 carbon atoms, a phenylene group or a naphthylene group, and the aliphatic alkylene group may also contain a hydroxyl group, an ether bond, an ester bond or a lactone ring;* 2 represents the atomic bonds to the carbon atoms of the backbone; Z 4 Each is independently a single bond, * 3 -Z 41 -C(=O)-O-,* 3 -C(=O)-NH-Z 41 -or* 3 -OZ 41 -;Z 41 is an alkylene group having 1 to 20 carbon atoms which may contain heteroatoms; * 3 Represents Z 3 Atomic bonds; Z 5 Each is independently a single bond, * 4 -Z 51 -C(=O)-O-,* 4 -C(=O)-NH-Z 51 -or* 4 -OZ 51 -;Z 51 is an alkylene group having 1 to 20 carbon atoms which may contain heteroatoms; * 4 Represents Z 4 Atomic bonds; Z 6 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, phenylene substituted with trifluoromethyl, * 2 -C(=O)-OZ 61 -, * 2 -C(=O)-N(H)-Z 61 -or* 2 -OZ 61 -;Z 61 It is an aliphatic alkylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group or a phenylene group substituted with a trifluoromethyl group, and may also contain a carbonyl group, an ester bond, an ether bond or a hydroxyl group;* 2 represents the atomic bonds to the carbon atoms of the backbone; R 31 and R 32 are each independently a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom; and R 31 and R 32 They may also bond to each other and form a ring together with the sulfur atom to which they are bonded; L 1 is a single bond, an ether bond, an ester bond, a carbonyl group, a sulfonate bond, a carbonate bond or a carbamate bond; R 1 and Rf 2 Each is independently a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; R 3 and Rf 4 Each is independently a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; R 5 and Rf 6 Each independently represents a hydrogen atom, a fluorine atom or a fluorinated saturated hydrocarbon group having 1 to 6 carbon atoms; but not all Rf 5 and Rf 6 At the same time, it is a hydrogen atom; M - It is a non-nucleophilic counter ion; A + is an onium cation; h is an integer from 0 to 3.

9. The chemically amplified positive resist composition according to claim 1, further comprising an organic solvent.

10. The chemically amplified positive resist composition according to claim 1, further comprising a fluorine-containing polymer containing at least one selected from the group consisting of a repeating unit represented by the following formula (D1), a repeating unit represented by the following formula (D2), a repeating unit represented by the following formula (D3), and a repeating unit represented by the following formula (D4), and further containing at least one selected from the group consisting of a repeating unit represented by the following formula (D5) and a repeating unit represented by the following formula (D6); In the formula, x is an integer from 1 to 3; y is an integer satisfying 0≤y≤5+2z-x; z is 0 or 1; w is an integer from 1 to 3; R B are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R C are each independently a hydrogen atom or a methyl group; R 101 , R 102 , R 104 and R 105 Each is independently a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms; R 103 , R 106 , R 107 and R 108 are each independently a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, a fluorinated hydrocarbon group having 1 to 15 carbon atoms, or an acid-labile group, and R 103 , R 106 , R 107 and R 108 When it is a hydrocarbon group or a fluorinated hydrocarbon group, the carbon-carbon bonds may be separated by ether bonds or carbonyl groups; R 109 A hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group between carbon-carbon bonds; R 110 It is a linear or branched hydrocarbon group having 1 to 5 carbon atoms, which may have a heteroatom-containing group between carbon-carbon bonds; R 111 is a saturated hydrocarbon group having 1 to 20 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and the -CH 2 -Part of it may also be substituted by an ester bond or an ether bond; W 1 A (w+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a (w+1)-valent fluorinated hydrocarbon group having 1 to 20 carbon atoms; W 2 is a single bond, *-C(=O)-O- or *-C(=O)-NH-; W 3 is a single bond, -O-, *-C(=O)-OW 31 -W 32 - or *-C(=O)-NH-W 31 -W 32 -;W 31 is a single bond or a saturated alkylene group having 1 to 10 carbon atoms; W 32 is a single bond, an ester bond, an ether bond or a sulfonamide bond; * indicates atomic bonds to carbon atoms of the backbone. 11 . The chemically amplified positive resist composition according to claim 1 , further comprising a quencher. 12 . The chemically amplified positive resist composition according to claim 1 , further comprising a photoacid generator other than the photoacid generator represented by formula (A).

13. A method for forming a resist pattern, comprising the following steps: A resist film is formed on a substrate using the chemically amplified positive resist composition according to any one of claims 1 to 12; the resist film is exposed using high-energy rays; and the exposed resist film is developed using an alkaline developer to obtain a resist pattern.

14. The resist pattern forming method according to claim 13, in, The high-energy rays are extreme ultraviolet rays or electron beams.

15. The resist pattern forming method according to claim 13, in, The outermost surface of the substrate is made of a material including at least one selected from the group consisting of chromium, silicon, tantalum, molybdenum, cobalt, nickel, tungsten, and tin.

16. The resist pattern forming method according to claim 13, in, The substrate is a transmissive or reflective mask blank.

17. A transmission type or reflection type blank mask coated with the chemically amplified positive resist composition according to any one of claims 1 to 12.

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