Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, method for producing electronic device, compound, resin

Abstract

The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern with excellent LWR performance. Also, a resin for an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern with excellent LWR performance and a compound as a monomer thereof are provided. Also, a resist film and a pattern forming method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device using the above-mentioned pattern forming method are provided. The actinic ray-sensitive or radiation-sensitive resin composition contains a resin X, and the resin X contains a repeating unit derived from the following compound. A compound: It contains two or more structural parts composed of an anion part and a cationic part and a polymerizable group, and generates an acid containing an acidic part derived from the above-mentioned anion part in the above-mentioned two or more structural parts by irradiation with actinic rays or radiation.

Description

Technical Field

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, a method for producing an electronic device, a compound and a resin. Background Art

[0002] In order to compensate for the decrease in sensitivity caused by light absorption after the KrF excimer laser (248nm) resist is used, a pattern forming method using chemical amplification is used. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposure part is decomposed by light irradiation to generate acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process, the alkali-insoluble groups of the resin contained in the photosensitive or radiation-sensitive resin composition are converted into alkali-soluble groups by the catalytic action of the generated acid, thereby changing the solubility in the developer. Thereafter, development is performed using, for example, an alkaline aqueous solution. Thus, the exposure part is removed to obtain the desired pattern.

[0003] In order to miniaturize semiconductor devices, the wavelength of exposure light sources has been shortened and the numerical aperture (NA) of projection lenses has been increased. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as light sources are being developed.

[0004] Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

[0005] For example, Patent Document 1 discloses an acid generator containing a salt represented by the following general formula (I) as a component used in a resist composition. In addition, such an acid generator is hereinafter also referred to as a "low-molecular acid generator".

[0006] [Chemical formula 1]

[0007]

[0008] Previous technical literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2019-14704 Summary of the invention

[0011] Technical issues to be solved by the invention

[0012] In the conventional resist composition, if the photoacid generator and the acid diffusion controller are added to the composition only as separate compounds, the photoacid generators or the acid diffusion controllers are easily condensed. Therefore, in the conventional resist composition, there are parts with high (or low) concentration of the photoacid generator and parts with high (or low) concentration of the acid diffusion controller in the formed resist film, which easily produces uneven concentration distribution of the photoacid generator and the acid diffusion controller. As a result, when the resist film is exposed, the amount and diffusion of the acid generated in the resist film are also uneven, which becomes the cause of uneven width of the pattern obtained after development.

[0013] In contrast, the low molecular weight acid generator disclosed in the prior art (e.g., Patent Document 1) contains both a site corresponding to a photoacid generator and a site corresponding to an acid diffusion controller in one molecule, and thus has the characteristic of being easy to make the existence ratio of each of the above sites constant in the resist film.

[0014] The present inventors have studied the resist composition described in Patent Document 1 and found that there is room for further improvement in the variation in pattern line width (LWR (line width roughness)) of a pattern formed using the resist composition.

[0015] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance.

[0016] Furthermore, the present invention aims to provide a resin used in an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance, and a compound as a monomer thereof.

[0017] Furthermore, the present invention aims to provide a resist film and a pattern forming method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device using the above-mentioned pattern forming method.

[0018] Means for solving technical problems

[0019] The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following structure.

[0020] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin X, wherein the resin X comprises a repeating unit derived from the following compound.

[0021] Compound: It contains two or more structural parts consisting of an anionic part and a cationic part and a polymerizable group,

[0022] An acid containing an acidic site derived from the anion site in the two or more structural sites is generated by irradiation with actinic rays or radiation.

[0023] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein

[0024] In the above compound, structures of two or more of the above anion sites are different from each other.

[0025] [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein:

[0026] The above compound is the compound (I) described later.

[0027] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein

[0028] The resin X further contains a repeating unit having an acid-decomposable group.

[0029] [5] An actinic ray-sensitive or radiation-sensitive resin composition comprising the following resin Y.

[0030] Resin Y: It contains:

[0031] Acid decomposable groups;

[0032] a group having a first structural part consisting of a first anion part and a first cation part; and

[0033] a group having a second structural part consisting of a second anion part and a second cation part,

[0034] The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation.

[0035] The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation.

[0036] The second acidic site has a structure different from that of the first acidic site, and its acid dissociation constant is larger than that of the first acidic site.

[0037] [6] The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein

[0038] The above resin Y contains:

[0039] A repeating unit comprising the above-mentioned acid-decomposable group; and

[0040] A repeating unit comprising a group having the first structural part and a group having the second structural part.

[0041] [7] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].

[0042] [8] A pattern forming method comprising the following steps:

[0043] A step of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition described in any one of [1] to [6];

[0044] a step of exposing the resist film to light; and

[0045] A step of developing the exposed resist film using a developer.

[0046] [9] A method for manufacturing an electronic device, comprising the pattern forming method described in [8].

[0047]

[10] A compound comprising two or more structural parts consisting of an anionic part and a cationic part and a polymerizable group,

[0048] An acid containing an acidic site derived from the anion site in the two or more structural sites is generated by irradiation with actinic rays or radiation.

[0049]

[11] The compound according to

[10] , wherein

[0050] Two or more of the anion sites described above have structures different from each other.

[0051]

[12] The compound according to

[10] or

[11] , which is the compound (I) described below.

[0052]

[13] A resin comprising a repeating unit derived from the compound described in any one of

[10] to

[12] .

[0053]

[14] The resin according to

[13] , further comprising a repeating unit having an acid-decomposable group.

[0054]

[15] A resin comprising:

[0055] Acid decomposable groups;

[0056] a group having a first structural part consisting of a first anion part and a first cation part; and

[0057] a group having a second structural part consisting of a second anion part and a second cation part,

[0058] The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation.

[0059] The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation.

[0060] The second acidic site has a structure different from that of the first acidic site, and its acid dissociation constant is larger than that of the first acidic site.

[0061]

[16] The resin according to

[15] , comprising:

[0062] A repeating unit comprising the above-mentioned acid-decomposable group; and

[0063] A repeating unit comprising a group having the first structural part and a group having the second structural part.

[0064] Effects of the Invention

[0065] According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in LWR performance can be provided.

[0066] Furthermore, according to the present invention, a resin used for an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance and a compound as a monomer thereof can be provided.

[0067] Furthermore, according to the present invention, a resist film and a pattern forming method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device using the above-mentioned pattern forming method can be provided. DETAILED DESCRIPTION

[0068] Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, method for producing an electronic device, compound, and resin according to the present invention will be described in detail.

[0069] The constituent elements described below will be described based on typical embodiments of the present invention, but the present invention is not limited to these embodiments.

[0070] In the marking of the group (atomic group) in this specification, unless it is contrary to the purpose of the present invention, the marking that does not record substitution and unsubstituted includes not only the group without substitution but also the group with substitution. For example, "alkyl" includes not only the alkyl without substitution (unsubstituted alkyl) but also the alkyl with substitution (substituted alkyl). In addition, the "organic group" in this specification refers to a group containing at least 1 carbon atom.

[0071] Unless otherwise specified, the substituent is preferably a monovalent substituent.

[0072] "Actinic rays" or "radiation" in this specification refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam), etc. "Light" in this specification refers to actinic rays or radiation.

[0073] Unless otherwise specified, "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), and X-rays, but also drawing using particle beams such as electron beams and ion beams.

[0074] In this specification, "to" is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0075] Unless otherwise specified, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in the compound represented by the general formula "XYZ" is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the above compound can be "X-CO-OZ" or "XO-CO-Z".

[0076] In the present specification, (meth)acrylate means acrylate and methacrylate, and (meth)acrylic acid means acrylic acid and methacrylic acid.

[0077] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene conversion values ​​obtained by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0078] In this specification, the acid dissociation constant (pKa) means the pKa in aqueous solution, specifically, the value obtained by calculation based on the database of Hammett's substituent constant and known literature values ​​using the following software package 1. The pKa values ​​described in this specification all represent the values ​​obtained by calculation using this software package.

[0079] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0080] On the other hand, pKa can also be calculated by molecular orbital algorithm. As a specific method, the calculation of H in aqueous solution based on thermodynamic cycle can be cited. + The method of calculating the dissociation free energy. + The calculation method of dissociation free energy can be calculated by DFT (density functional method), for example, but various other methods have been reported in literature, etc., and the method is not limited to this. In addition, there are many software that can realize DFT, for example, Gaussian16 can be cited.

[0081] As described above, the pKa in this specification refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values ​​using Software Package 1, but when pKa cannot be calculated by this method, a value obtained by Gaussian16 based on DFT (density functional method) is used.

[0082] As described above, the pKa in this specification refers to "pKa in an aqueous solution", but when the pKa in an aqueous solution cannot be calculated, the "pKa in a dimethyl sulfoxide (DMSO) solution" is used.

[0083] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0084] Hereinafter, after describing the compound and resin of the present invention, an actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device will be described.

[0085] [Compound]

[0086] The compound of the present invention (hereinafter also referred to as "specific compound") contains two or more structural parts consisting of an anion part and a cation part and a polymerizable group.

[0087] An acid containing an acidic site derived from the anion site in the two or more structural sites is generated by irradiation with actinic rays or radiation.

[0088] An actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition") containing a resin X containing a repeating unit derived from the above-mentioned specific compound (hereinafter also referred to as "specific resin X") can form a pattern excellent in LWR performance.

[0089] Although its mechanism of action is not necessarily clear, the present inventors speculate as follows.

[0090] According to the research conducted by the present inventors, it has been found that the low molecular weight acid generator disclosed in the prior art (e.g., Patent Document 1) is easily aggregated in the composition. Due to this aggregation, the uniformity of the existence ratio of the site corresponding to the photoacid generator and the site corresponding to the acid diffusion controller in the resist film may sometimes cause the LWR performance of the formed pattern to fail to meet the desired requirements.

[0091] In contrast, the above-mentioned specific resin X has more than two structural parts consisting of an anion part and a cation part. Therefore, when at least one of the structural parts is used as a structural part X having a function equivalent to a photoacid generator, and at least one of the structural parts is used as a structural part Y having a function equivalent to an acid diffusion controller, since the structural part equivalent to the photoacid generator and the structural part equivalent to the acid diffusion controller are both included in one molecule, the existence ratio of each of the above-mentioned structural parts can be made constant in the resist film. In particular, the above-mentioned specific resin is a structure in which a salt structural part (a structural part consisting of an anion part and a cation part and equivalent to the above-mentioned structural part X and the above-mentioned structural part Y) that is easy to condense is carried on the resin, so it is difficult to condense in the composition compared with the low molecular weight acid generator disclosed in Patent Document 1. That is, compared with the low molecular weight acid generator disclosed in Patent Document 1, by using the above-mentioned specific resin X, it is easier to further maintain the uniformity of the existence ratio of the structural part equivalent to the photoacid generator and the structural part equivalent to the acid diffusion controller. As a result, even when the resist film is exposed, the amount and diffusion of acid generated in the resist film tend to be uniform, and the width of the pattern obtained after development tends to be stable (that is, the LWR performance of the pattern is excellent). This is known, for example, from the results of Comparative Examples 1-3 in the Examples column.

[0092] In addition, in the low-molecular-weight acid generator disclosed in Patent Document 1, since the diffusion distance of the acid generated by irradiation with actinic rays or radiation is large, the EL performance of the composition containing the low-molecular-weight acid generator may be poor.

[0093] In contrast, the present inventors have also found that the EL performance of the resist composition is further improved by a resin containing a repeating unit derived from a specific compound that can generate a polymerizable group, an acidic site derived from the anionic site in the structural site X, and an acidic site derived from the anionic site in the structural site Y by irradiation with actinic rays or radiation (hereinafter also referred to as "specific resin XA") in the specific resin X. Although the mechanism of action is not necessarily clear, the present inventors presume as follows.

[0094] The repeating unit derived from the above-mentioned specific compound in the above-mentioned specific resin XA can function as an acidic site that generates acid by irradiation with actinic rays or radiation. That is, the above-mentioned specific resin XA can form an acidic site derived from the anionic site in the above-mentioned structural site X and an acidic site derived from the anionic site in the above-mentioned structural site Y in the resin by irradiation with actinic rays or radiation. That is, these acidic sites after exposure are in a state supported in the specific resin XA, so compared with the low-molecular acid generator disclosed in patent document 1, the diffusion distance is significantly smaller. As a result, the EL performance of the resist composition containing the above-mentioned specific resin XA is also excellent. This point can also be known from the results of Examples 1-10, etc. in the Example column, for example.

[0095] Furthermore, the present inventors have found that a resist composition containing the following resin Y (hereinafter also referred to as "specific resin Y") can form a pattern having excellent LWR performance by the same mechanism of action as the above-mentioned specific resin XA, and also has excellent EL performance.

[0096] Resin Y: It contains:

[0097] Acid decomposable groups;

[0098] a group having a first structural part consisting of a first anion part and a first cation part; and

[0099] a group having a second structural part consisting of a second anion part and a second cation part,

[0100] The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation.

[0101] The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation.

[0102] The second acidic site has a structure different from that of the first acidic site, and its acid dissociation constant is larger than that of the first acidic site.

[0103] Hereinafter, after describing the specific compound, the specific resin X, and the specific resin Y, the resist composition will be described.

[0104] The specific compound contains a polymerizable group.

[0105] The type of the polymerizable group is not particularly limited, but a functional group capable of addition polymerization is preferred, a polymerizable ethylenically unsaturated group or a cyclopolymerizable group is more preferred, and a polymerizable ethylenically unsaturated group is further preferred.

[0106] Specific examples of the polymerizable ethylenically unsaturated group include a (meth)acryloyl group, a vinyl group, a styryl group, and a group represented by the following general formula (W1).

[0107] Examples of the ring polymerizable group include an epoxy group and an oxetanyl group.

[0108] The number of polymerizable groups in the specific compound is not particularly limited, but is preferably 1 to 3, and more preferably 1.

[0109] [Chemical formula 2]

[0110]

[0111] In the above general formula (W1), W 1 represents a compound selected from -C(R 11 )2-、-N(R 12 )-, -O- and >C(=O) formed by the radicals. 11 and R 12 Each independently represents a hydrogen atom or a monovalent substituent.

[0112] As R 11 and R 12 The monovalent substituent represented by is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

[0113] As R 11 and R 12 , among which a hydrogen atom is preferred.

[0114] In the above general formula (W1), the ring represented by T represents the carbon atom indicated in the general formula (W1) and the ring represented by W. 1 The atomic group represented forms a ring with 5 to 7 ring member atoms.

[0115] The ring represented by T is preferably a ring having 5 or 6 ring members (in other words, a 5-membered ring or a 6-membered ring).

[0116] In the above general formula (W1), * represents a bonding position. 1 The hydrogen atoms in the atomic group represented by form the bonding positions represented by *.

[0117] The specific compound contains two structural sites consisting of an anion site and a cation site (hereinafter also referred to as "specific structural site").

[0118] In the above-mentioned specific structural parts, the anion part and the cation part have equal valence and exist in pairs. Here, the anion part is a structural part containing an atom or an atomic group with a negative charge, and the cation part is a structural part containing an atom or an atomic group with a positive charge.

[0119] The specific compound generates an acid containing an acidic site derived from the anion site in the above-mentioned two or more specific structural sites by irradiation with actinic rays or radiation. That is, for example, when the specific compound has structural site X and structural site Y as specific structural sites, the generated acid contains an acidic site derived from the anion site in structural site X and an acidic site derived from the anion site in structural site Y. Among them, the generated acid preferably contains an acidic site and a polymerizable group derived from the anion site in the above-mentioned two or more specific structural sites. That is, for example, when the specific compound has structural site X and structural site Y as specific structural sites, the generated acid contains an acidic site derived from the anion site in structural site X, an acidic site derived from the anion site in structural site Y, and a polymerizable group. As described above, when the generated acid contains a polymerizable group, the resin containing a repeating unit derived from the above-mentioned specific compound (i.e., equivalent to the above-mentioned resin XA) can form an acidic site derived from the anion site in structural site X and an acidic site derived from the anion site in structural site Y in the resin by irradiation with actinic rays or radiation. As a result, the resist composition containing the resin including the repeating unit derived from the specific compound is excellent in EL performance.

[0120] In the specific compound, the specific structural site is preferably a site represented by the following general formula (D1) or the following general formula (D2). X1- and P2 X2- Equivalent to the anion site. And, Q1 X1+ and Q2 X2+ Equivalent to the cationic site.

[0121] [Chemical formula 3]

[0122]

[0123] In the general formula (D1), P1 X1- Indicates a negatively charged atomic group with a valence of X1. X1+ Indicates a positively charged atomic group with a valence of X1. *Indicates a bonding position.

[0124] In the general formula (D1), P2 X2- Represents a negatively charged atomic group with a valence of X2. X2+Indicates a positively charged atomic group with a valence of X2. *Indicates a bonding position.

[0125] In the general formula (D1) and the general formula (D2), the valence number represented by X1 and X2 is not particularly limited, but is preferably 1.

[0126] In the general formula (D1) and the general formula (D2), as P1 X1- and P2 X2- The negatively charged atomic group represented by is preferably, for example, an anionic functional group described later.

[0127] In the general formula (D1) and the general formula (D2), as Q1 X1+ and Q2 X2+ The positively charged atomic group represented by is preferably, for example, an organic cation described later.

[0128] In addition, when the specific structural site is, for example, a site represented by the general formula (D1) or the general formula (D2), and the valences represented by X1 and X2 in the general formula (D1) or the general formula (D2) are 1 respectively, by irradiation with actinic rays or radiation, a structure derived from P1 is formed. X1- and P2 X2- The anion site represented by the general formula (D1-H) and the acidic site represented by the general formula (D2-H).

[0129] [Chemical formula 4]

[0130] *-P1H (D1-H)

[0131] *-P2H-* (D2-H)

[0132] The number of specific structural sites in the specific compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 4, and more preferably 2.

[0133] As the specific compound, a compound represented by the following general formula (S1) or the following general formula (S2) is preferred.

[0134] [Chemical formula 5]

[0135]

[0136] In the general formula (S1), W 11 represents a polymerizable group. The polymerizable group is as described above.

[0137] L 11 and L 12 Each independently represents a single bond or a divalent linking group.

[0138] As L 11 and L 12The divalent linking group represented by the invention is not particularly limited, and examples thereof include -CO-, -NR A -, -O-, alkylene (preferably having 1 to 6 carbon atoms. It may be straight chain or branched.), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and further preferably a 5- to 6-membered ring), and a divalent linking group formed by combining a plurality of them. The above R A Examples thereof include a hydrogen atom and a monovalent substituent. The monovalent substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 6 carbon atoms and may be linear or branched).

[0139] Furthermore, the alkylene group, the cycloalkylene group, the alkenylene group, and the divalent aliphatic heterocyclic group may be substituted with a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom).

[0140] As L 11 Among them, a single bond or a divalent linking group consisting of one or more selected from -O- and an alkylene group (preferably having 1 to 6 carbon atoms and may be linear or branched) is preferred.

[0141] As L 12 Among them, a single bond or an alkylene group substituted by a fluorine atom is preferred (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. It can be linear or branched.), a single bond or an alkylene group substituted by a fluorine atom is more preferred, and a perfluoroalkylene group is further preferred.

[0142] D 11 It represents a group represented by the above-mentioned general formula (D2).

[0143] D 12 It represents a group represented by the above-mentioned general formula (D1).

[0144] In the general formula (S2), W 21 represents a polymerizable group. The polymerizable group is as described above.

[0145] L 21 It represents a trivalent linking group.

[0146] As L 21 The trivalent linking group represented by is not particularly limited, but examples thereof include groups represented by the following general formula (LX).

[0147] [Chemical formula 6]

[0148]

[0149] In the general formula (LX), L 31 represents a trivalent linking group. 32 , L 33 and L 34 Each independently represents a single bond or a divalent linking group. *1 represents the 21 The bonding position of D 21 The bonding position of D 22 bonding position.

[0150] As L 31 The trivalent linking group represented by is not particularly limited, but examples thereof include C(R B ), a nitrogen atom, a trivalent hydrocarbon ring group, a trivalent heterocyclic group, and the like.

[0151] The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14.

[0152] The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring.

[0153] R B represents a hydrogen atom or a monovalent substituent.

[0154] As R B The monovalent substituent represented by is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 6 carbon atoms, and may be linear or branched).

[0155] As L 31 , among which CH is preferred.

[0156] As L 32 , L 33 and L 34 The divalent linking group represented by the invention is not particularly limited, and examples thereof include -CO-, -NR A -, -O-, alkylene (preferably having 1 to 6 carbon atoms. It may be straight chain or branched.), cycloalkylene (preferably having 3 to 15 carbon atoms), alkenylene (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and further preferably a 5- to 6-membered ring), and a divalent linking group formed by combining a plurality of them. The above R AExamples thereof include a hydrogen atom and a monovalent substituent. The monovalent substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 6 carbon atoms and may be linear or branched).

[0157] Furthermore, the alkylene group, the cycloalkylene group, the alkenylene group, and the divalent aliphatic heterocyclic group may be substituted with a substituent, and examples of the substituent include a halogen atom (preferably a fluorine atom).

[0158] As L 33 , among which a single bond or -O- is preferred.

[0159] As L 32 and L 34 Among them, a single bond or an alkylene group (preferably having 1 to 6 carbon atoms and may be linear or branched) is preferred.

[0160] D 21 and D 22 Each independently represents a group represented by the above-mentioned general formula (D1).

[0161] Next, for the above general formula (D1) and general formula (D2), P1 X1- and P2 X2- The negatively charged atomic groups are described below.

[0162] As P1 X1- and P2 X2- The negatively charged atomic group represented by - and as a part having -SO3 - The group, -COO - and as a part of -COO - A group having -N as a part - -group and having as a part a carbanion (-C - <) group.

[0163] As P1 X1- Among them, groups represented by the following general formulae (B-1) to (B-13) are preferred.

[0164] [Chemical formula 7]

[0165]

[0166] In general formulae (B-1) to (B-13), * represents a bonding position.

[0167] In addition, * in the general formula (B-12) is also preferably a bonding position to a group other than -CO- and -SO2-.

[0168] In the general formulas (B-1) to (B-5) and (B-12), R X1 Represents an organic group.

[0169] As R X1 , preferably an alkyl group (which may be linear or branched, and preferably has 1 to 15 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms), or an aryl group (which may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms).

[0170] In the general formula (B-5), R X1 in and N - The directly bonded atom is also preferably not any of the carbon atom in -CO- and the sulfur atom in -SO2-.

[0171] R X1 The cycloalkyl group in the group may be a monocyclic ring or a polycyclic ring.

[0172] As R X1 Examples of the cycloalkyl group include norbornyl and adamantyl.

[0173] R X1 The substituent that the cycloalkyl group in may have is preferably an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms).

[0174] R X1 One or more of the carbon atoms serving as ring atoms of the cycloalkyl group may be substituted by a carbonyl carbon atom.

[0175] R X1 The number of carbon atoms of the alkyl group in the group is preferably 1-10, more preferably 1-5.

[0176] R X1 The substituent that the alkyl group in the group may have is preferably a cycloalkyl group, a fluorine atom or a cyano group.

[0177] Examples of the cycloalkyl group as the above substituent include: X1 In the case of a cycloalkyl group, the cycloalkyl group described above.

[0178] R X1 When the alkyl group in has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group.

[0179] And, R X1 In the alkyl group, one or more -CH2- groups may be substituted by a carbonyl group.

[0180] R X1 The aryl group in is preferably a benzene ring group.

[0181] RX1 The substituent that the aryl group in the formula (A) may have is preferably an alkyl group, a fluorine atom or a cyano group. Examples of the alkyl group as the substituent include: X1 The alkyl group described in the case of a cycloalkyl group is preferably a perfluoroalkyl group, and more preferably a perfluoromethyl group.

[0182] In the general formulas (B-7) and (B-11), R X2 represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.

[0183] By R X2 The substituent other than the fluorine atom and the perfluoroalkyl group represented by is preferably an alkyl group other than the perfluoroalkyl group or a cycloalkyl group.

[0184] Examples of the above alkyl group include: X1 The alkyl group in the above-mentioned group is substituted by the alkyl group of the perfluoroalkyl group. In addition, the above-mentioned alkyl group preferably has no fluorine atom.

[0185] Examples of the cycloalkyl group include: X1 In addition, the cycloalkyl group preferably has no fluorine atom.

[0186] In the general formula (B-8), R XF1 represents a hydrogen atom, a fluorine atom or a perfluoroalkyl group. XF1 At least one of them represents a fluorine atom or a perfluoroalkyl group.

[0187] By R XF1 The perfluoroalkyl group represented by is preferably 1-15, more preferably 1-10, and even more preferably 1-6.

[0188] In the general formula (B-10), R XF2 represents a fluorine atom or a perfluoroalkyl group.

[0189] By R XF2 The perfluoroalkyl group represented by is preferably 1-15, more preferably 1-10, and even more preferably 1-6.

[0190] In the general formula (B-9), n represents an integer of 0-4.

[0191] As P2 X2- Among them, groups represented by the following general formulae (C-1) to (C-19) are preferred.

[0192] [Chemical formula 8]

[0193]

[0194] [Chemical formula 9]

[0195]

[0196] It is preferred that the structures of two or more anionic sites (anionic functional groups) contained in the specific compound are different from each other.

[0197] There is no particular limitation on the combination of anionic sites (anionic functional groups), and preferred examples include a combination of general formula (B-10) and general formula (C-1), a combination of general formula (B-10) and general formula (C-8), a combination of general formula (C-1) and general formula (B-8), a combination of general formula (C-1) and general formula (B-1), or a combination of general formula (B-2) and general formula (B-6). In the case of the above combination, the difference in acid dissociation constants of the acidic sites derived from each anionic site becomes more appropriate, and the LWR performance of the formed pattern is more excellent.

[0198] As Q1 in the general formula (D1) and the general formula (D2) X1+ and Q2 X2+ The positively charged atomic group represented by is preferably an organic cation shown below.

[0199] By Q1 X1+ and Q2 X2+ The organic cations represented are each independently preferably an organic cation represented by the general formula (ZaI) (cation (ZaI)) or an organic cation represented by the general formula (ZaII) (cation (ZaII)).

[0200] [Chemical formula 10]

[0201]

[0202] R 204 -| + -R 205 (ZaII)

[0203] In the above general formula (ZaI),

[0204] R 201 , R 202 and R 203 Each independently represents an organic group.

[0205] As R 201 , R 202 and R 203 The number of carbon atoms of the organic group is usually 1 to 30, preferably 1 to 20. 201 ~R 203 Two of them may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring. 201 ~R 203Examples of the group formed by bonding two of the groups include an alkylene group (e.g., a butylene group and a pentylene group) and -CH2-CH2-O-CH2-CH2-.

[0206] Preferred forms of the organic cation in the general formula (ZaI) include the cation (ZaI-1) and cation (ZaI-2) described later, the organic cation represented by the general formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by the general formula (ZaI-4b) (cation (ZaI-4b)).

[0207] First, the cation (ZaI-1) will be described.

[0208] The cation (ZaI-1) is R 201 ~R 203 At least one of the arylsulfonium cations is an aryl group.

[0209] In the arylsulfonium cation, R 201 ~R 203 All are aromatic, and R 201 ~R 203 Part of them is aryl, and the rest is alkyl or cycloalkyl.

[0210] And, R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group in the ring. 201 ~R 203 In the group formed by two bonds, for example, one or more methylene groups may be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group and / or a carbonyl group (for example, a butylene group, a pentylene group or -CH2-CH2-O-CH2-CH2-).

[0211] Examples of the arylsulfonium cation include a triarylsulfonium cation, a diarylalkylsulfonium cation, an aryldialkylsulfonium cation, a diarylcycloalkylsulfonium cation, and an aryldicycloalkylsulfonium cation.

[0212] As the aryl group contained in the arylsulfonium cation, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. As the heterocyclic structure, pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues and benzothiophene residues can be cited. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.

[0213] The alkyl group or cycloalkyl group that the arylsulfonium cation has as required is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0214] As R 201 ~R 203 The substituents that the aryl, alkyl and cycloalkyl groups may have include, independently, alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and phenylthio groups.

[0215] The above-mentioned substituent may further have a substituent if possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group.

[0216] Next, the cation (ZaI-2) will be described.

[0217] The cation (ZaI-2) is R in the formula (ZaI) 201 ~R 203 Each independently represents a cation of an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.

[0218] As R 201 ~R 203 The organic group having no aromatic ring usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0219] R 201 ~R 203 Each independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, and further preferably a linear or branched 2-oxoalkyl group.

[0220] As R 201 ~R 203 The alkyl and cycloalkyl groups include, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0221] R 201 ~R 203It may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

[0222] Next, the cation (ZaI-3b) will be described.

[0223] The cation (ZaI-3b) is a cation represented by the following general formula (ZaI-3b).

[0224] [Chemical formula 11]

[0225]

[0226] In the general formula (ZaI-3b),

[0227] R 1c ~R 5c Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.

[0228] R 6c and R 7c Each independently represents a hydrogen atom, an alkyl group (such as tert-butyl group), a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

[0229] R x and R y Each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

[0230] R 1c ~R 5c Any two or more of R 5c With R 6c , R 6c With R 7c , R 5c With R x and R x With R y They may be bonded to form a ring, and the ring may independently contain an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amide bond.

[0231] Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0232] As R 1c ~R 5c Any two or more of R 6c With R 7c and Rx With R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted with a hetero atom such as an oxygen atom.

[0233] As R 5c With R 6c and R 5c With R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0234] Next, the cation (ZaI-4b) will be described.

[0235] The cation (ZaI-4b) is a cation represented by the following general formula (ZaI-4b).

[0236] [Chemical formula 12]

[0237]

[0238] In the general formula (ZaI-4b),

[0239] l represents an integer from 0 to 2.

[0240] r represents an integer from 0 to 8.

[0241] R 13 The group represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent.

[0242] R 14 represents a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may also have a substituent. 14 , each independently represents the above-mentioned groups such as hydroxyl group.

[0243] R 15 Each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may also have a substituent. 15 Can bond to each other to form a ring. 15 When they are bonded to each other to form a ring, heteroatoms such as oxygen atoms and nitrogen atoms may be contained in the ring skeleton. 15 are alkylene groups, and are bonded to each other to form a ring structure.

[0244] In the general formula (ZaI-4b), R 13 , R14 and R 15 The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, or the like is more preferred.

[0245] Next, the general formula (ZaII) will be described.

[0246] In the general formula (ZaII), R 204 and R 205 Each independently represents an aryl group, an alkyl group or a cycloalkyl group.

[0247] As R 204 and R 205 R is an aryl group, preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group containing a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group containing a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0248] As R 204 and R 205 The alkyl group and cycloalkyl group are preferably a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl) or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl or norbornyl).

[0249] R 204 and R 205 The aryl group, alkyl group and cycloalkyl group of R may each independently have a substituent. 204 and R 205 The aryl group, alkyl group and cycloalkyl group may have a substituent, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group and a phenylthio group.

[0250] The specific compound is also preferably the following compound (I): In the following compound (I), the structures of two or more anionic sites among the anionic sites (anionic functional groups) in the compound are different from each other, and the acid dissociation constants of the acidic sites derived from these anionic sites are also different from each other.

[0251] In addition, the following compound (I) further contains a polymerizable group, and the type of the polymerizable group and its preferred embodiment are as described above.

[0252] Compound (I): having at least one of each of the following structural part X and the following structural part Y, and having a polymerizable group, wherein the compound generates an acid containing the above-mentioned polymerizable group, the following first acidic part derived from the following structural part X, and the following second acidic part derived from the following structural part Y upon irradiation with actinic rays or radiation.

[0253] Structural site X: Anionic site A1 - and cationic site M1 + The first acidic site represented by HA1 is formed by irradiation with actinic rays or radiation.

[0254] Structural site Y: Anionic site A2 - and cationic site M2 + The structure of the second acidic site represented by HA2 having a different structure from the first acidic site formed in the structure site X is formed by irradiation with actinic rays or radiation.

[0255] Among them, compound (I) satisfies the following condition I.

[0256] Condition I: In the above compound (I), the cationic site M1 in the above structural site X is + and the cationic site M2 in the structural site Y + Replaced by H + The compound PI has an acid dissociation constant a1, which is derived from the cationic site M1 in the structural site X. + Replaced by H + and an acid dissociation constant a2 derived from the cationic site M2 in the structural site Y. + Replaced by H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0257] Furthermore, the compound PI described above corresponds to an acid generated by irradiating compound (I) with actinic rays or radiation.

[0258] In addition, the acid dissociation constant a1 and the acid dissociation constant a2 are obtained by the above method. Regarding the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI, more specifically, when the acid dissociation constant of the compound PI is obtained, the compound PI (the compound PI is equivalent to the "compound having a polymerizable group, HA1 and HA2"). becomes the "compound having a polymerizable group, A1 - and HA2" is the acid dissociation constant a1, and the above-mentioned "compound having a polymerizable group, A1 -and HA2" becomes "a compound having a polymerizable group, A1 - and A2 - The pKa of the compound is the acid dissociation constant a2.

[0259] In terms of better LWR performance of the formed pattern, in the above-mentioned compound PI, the difference between the acid dissociation constant a1 and the above-mentioned acid dissociation constant a2 is preferably 0.10 or more, and more preferably 2.0 or more. In addition, the upper limit of the difference between the acid dissociation constant a1 and the above-mentioned acid dissociation constant a2 is not particularly limited, for example, it is preferably 15.0 or less.

[0260] In the above compound PI, the acid dissociation constant a2 is preferably 6.5 or less, more preferably 3.0 or less, and further preferably 1.0 or less in terms of the excellent stability of the cationic site of compound (I) in the resist composition. In addition, the lower limit of the acid dissociation constant a2 is preferably -4.5 or more.

[0261] Furthermore, from the viewpoint of better LWR performance of the formed pattern, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0.5 or less, and further preferably -0.1 or less. The lower limit of the acid dissociation constant a1 is preferably -15.0 or more.

[0262] Specifically, the structural portion X and the structural portion Y correspond to the above-mentioned specific structural portion.

[0263] Specific examples of the compound (I) include the compound of the general formula (S1) (wherein D 11 and D 12 In which the valence numbers represented by X1 and X2 are 1 respectively) and the above-mentioned general formula (S2) (wherein, D 21 and D 22 In the formula (S1), the valences represented by X1 and X2 are 1 respectively). That is, the structural part X and the structural part Y in the compound (I) correspond to D in the general formula (S1) above. 11 and D 12 Furthermore, the structural part X and the structural part Y in the compound (I) correspond to D in the above general formula (S2). 21 and D 22 One and the other.

[0264] By appropriately selecting the anionic part (anionic functional group) in the structural part X and the structural part Y in the compound (I), the acid dissociation constant a1 and the acid dissociation constant a2 can be set within a predetermined range.

[0265] As anionic site A1 -With anionic site A2 - Combinations of, for example, preferably a combination of the above-mentioned general formula (B-10) with the above-mentioned general formula (C-1), a combination of the above-mentioned general formula (B-10) with the above-mentioned general formula (C-8), a combination of the above-mentioned general formula (C-1) with the above-mentioned general formula (B-8), a combination of the above-mentioned general formula (C-1) with the above-mentioned general formula (B-1) or a combination of the above-mentioned general formula (B-2) with the above-mentioned general formula (B-6).

[0266] The specific compound can be synthesized according to a known synthesis method.

[0267] A specific example of the specific compound is shown below.

[0268] [Chemical formula 13]

[0269]

[0270] [Chemical formula 14]

[0271]

[0272] [Resin]

[0273] The resin of the present invention is described below. The resin of the present invention is as follows.

[0274] Specific resin X (first embodiment):

[0275] A resin containing a repeating unit derived from the above-mentioned specific compound (hereinafter also referred to as a "specific repeating unit").

[0276] Specific resin Y (second embodiment):

[0277] A resin comprising:

[0278] Acid decomposable groups;

[0279] A group having a first structural part composed of a first anion part and a first cationic part (hereinafter also referred to as "a group containing a first structural part"); and

[0280] A group having a second structural part consisting of a second anion part and a second cation part (hereinafter also referred to as "a group containing a second structural part"), wherein

[0281] The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation.

[0282] The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation.

[0283] The second acidic site has a structure different from that of the first acidic site, and an acid dissociation constant thereof is larger than that of the first acidic site.

[0284] [Specific resin X (first embodiment)]

[0285] The specific resin X contains a repeating unit (specific repeating unit) derived from the above-mentioned specific compound.

[0286] The content of the specific repeating unit is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more, relative to all repeating units in the specific resin X. The upper limit thereof is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0287] The specific resin X is preferably a resin that is decomposed by the action of an acid and has increased polarity (hereinafter also referred to as an "acid-decomposable resin").

[0288] That is, when the specific resin X is an acid-decomposable resin, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0289] The specific resin X generally contains a group that is decomposed by the action of an acid to increase polarity (hereinafter, also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group.

[0290] <Repeating unit having an acid-decomposable group>

[0291] The acid-decomposable group refers to a group that generates a polar group by decomposition by the action of an acid. The acid-decomposable group preferably has a structure in which the polar group is protected by a dissociating group that is dissociated by the action of an acid. That is, the specific resin X preferably contains a repeating unit having a group that generates a polar group by decomposition by the action of an acid. The polarity of the resin having the repeating unit increases by the action of an acid, thereby increasing the solubility in an alkaline developer and reducing the solubility in an organic solvent.

[0292] The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris(alkylcarbonyl) methylene group, and a tris(alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.

[0293] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0294] Examples of the leaving group that leaves by the action of an acid include groups represented by formulae (Y1) to (Y4).

[0295] Formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0296] Formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0297] Formula (Y3): -C(R 36 )(R 37 )(OR 38 )

[0298] Formula (Y4): -C(Rn)(H)(Ar)

[0299] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (straight chain or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight chain or branched), or an aryl group (monocyclic or polycyclic). When possible, these groups also preferably have a fluorine atom or a group having a fluorine atom as a substituent.

[0300] When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferred that at least two of Rx1 to Rx3 are methyl groups.

[0301] Among them, it is preferred that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferred that Rx1 to Rx3 each independently represent a linear alkyl group.

[0302] Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring.

[0303] The alkyl group for Rx1 to Rx3 is preferably an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group.

[0304] The cycloalkyl group for Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0305] As the aryl group for Rx1 to Rx3, an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include phenyl, naphthyl, and anthracenyl.

[0306] As the alkenyl group of Rx1 to Rx3, a vinyl group is preferable.

[0307] The ring formed by two of Rx1 to Rx3 being bonded together is preferably a cycloalkyl group. The cycloalkyl group formed by two of Rx1 to Rx3 being bonded together is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0308] In the cycloalkyl group formed by bonding two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be substituted by a group having a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkyl ring may be substituted by a vinylene group.

[0309] The group represented by the formula (Y1) or (Y2) is also preferably a mode in which, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0310] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 With R 38 They may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. 36 A hydrogen atom is also preferred.

[0311] Furthermore, the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups may also contain groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the above-mentioned alkyl, cycloalkyl, aryl and aralkyl groups, for example, one or more methylene groups may be substituted by groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0312] And, R 38 R may bond with another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by bonding with another substituent possessed by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0313] As the formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0314] [Chemical formula 15]

[0315]

[0316] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these groups (for example, a group formed by combining an alkyl group and an aryl group).

[0317] M represents a single bond or a divalent linking group.

[0318] Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group formed by combining these groups (for example, a group formed by combining an alkyl group and a cycloalkyl group).

[0319] In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

[0320] It is also preferred that one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group.

[0321] At least two of Q, M and L1 may be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0322] From the viewpoint of pattern miniaturization, L2 is preferably a secondary alkyl group or a tertiary alkyl group, and more preferably a tertiary alkyl group. As the secondary alkyl group, isopropyl, cyclohexyl or norbornyl can be mentioned, and as the tertiary alkyl group, tert-butyl or adamantyl can be mentioned. In these modes, since Tg (glass transition temperature) and activation energy increase, it is possible to ensure film strength and suppress blurring.

[0323] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0324] From the viewpoint of excellent acid decomposability of the repeating unit, it is also preferred that when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group protecting a polar group, the ring atoms in the non-aromatic ring adjacent to the ring atoms directly bonded to the polar group (or its residue) do not have a halogen atom such as a fluorine atom as a substituent.

[0325] In addition, the leaving group that is released by the action of the acid may be a 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (alkyl group, etc.) such as a 1,1,4,4-tetramethylcyclohexyl group.

[0326] As the repeating unit having an acid-decomposable group, a repeating unit represented by the formula (A) is also preferred.

[0327] [Chemical formula 16]

[0328]

[0329] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom, R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, and R2 represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. At least one of L1, R1, and R2 has a fluorine atom or an iodine atom.

[0330] L1 represents a divalent linking group that may have a fluorine atom or an iodine atom. As a divalent linking group that may have a fluorine atom or an iodine atom, -CO-, -O-, -S-, -SO-, -SO2-, a hydrocarbon group (e.g., an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.) that may have a fluorine atom or an iodine atom, and a linking group formed by connecting a plurality of them, etc., can be cited. Among them, as L1, preferably -CO- or -arylene-alkylene- having a fluorine atom or an iodine atom.

[0331] The arylene group is preferably a phenylene group.

[0332] The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0333] The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0334] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.

[0335] The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0336] The total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0337] The above-mentioned alkyl group may contain heteroatoms such as oxygen atoms other than halogen atoms.

[0338] R2 represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom.

[0339] Examples of the leaving group include groups represented by the above formulae (Y1) to (Y4).

[0340] As the repeating unit having an acid-decomposable group, for example, the repeating units described in paragraphs

[0068] to

[0108] of JP-A-2014-010245 can also be used, and the contents thereof are incorporated into the present specification.

[0341] The content of the repeating unit having an acid-decomposable group is preferably 15 to 95 mol % based on all the repeating units in the specific resin X, more preferably 30 to 80 mol %, and even more preferably 30 to 70 mol %.

[0342] <Repeating unit having a lactone group, a sultone group or a carbonate group>

[0343] The specific resin X may include a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group (hereinafter also collectively referred to as a "repeating unit having a lactone group, a sultone group, or a carbonate group").

[0344] It is also preferred that the repeating unit having a lactone group, a sultone group or a carbonate group does not have an acid group such as a hexafluoropropanol group.

[0345] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, a structure in which another ring structure is fused to a 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure, or a structure in which another ring structure is fused to a 5- to 7-membered ring sultone structure in the form of a bicyclic structure or a spirocyclic structure is more preferably used.

[0346] The specific resin X preferably contains a repeating unit having a lactone group or a sultone group formed by extracting one or more hydrogen atoms from ring atoms of a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3).

[0347] Furthermore, the lactone group or the sultone group may be directly bonded to the main chain. For example, the main chain of the specific resin X may be constituted by the ring member atoms of the lactone group or the sultone group.

[0348] [Chemical formula 17]

[0349]

[0350] The lactone structure or sultone structure may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, multiple Rb2 may be different, and multiple Rb2 may be bonded to each other to form a ring.

[0351] Examples of the repeating unit containing a group having a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21) or a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3) include repeating units represented by the following general formula (AI).

[0352] [Chemical formula 18]

[0353]

[0354] In the general formula (AI), Rb0 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0355] Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom.

[0356] Examples of the halogen atom of Rb0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb0 is preferably a hydrogen atom or a methyl group.

[0357] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining them. Among them, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0358] V represents a group formed by extracting one hydrogen atom from a ring atom of a lactone structure represented by any of the general formulae (LC1-1) to (LC1-21), or a group formed by extracting one hydrogen atom from a ring atom of a sultone structure represented by any of the general formulae (SL1-1) to (SL1-3).

[0359] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Furthermore, one optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0360] As the carbonate group, a cyclic carbonate group is preferred.

[0361] As the repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferred.

[0362] [Chemical formula 19]

[0363]

[0364] In the general formula (A-1), R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

[0365] n represents an integer greater than or equal to 0.

[0366] R A 2 represents a substituent. When n is 2 or more, there are multiple R A 2 They may be the same or different.

[0367] A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of a combination thereof.

[0368] Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0369] As the repeating unit having a lactone group or a sultone group, for example, the repeating units described in paragraphs

[0109] to

[0120] of JP-A-2014-010245 can also be used, and the contents thereof are incorporated into the present specification.

[0370] As the repeating unit having a carbonate group, for example, the repeating units described in paragraphs

[0121] to

[0132] of JP-A-2014-010245 can also be used, and the contents thereof are incorporated into the present specification.

[0371] The content of the repeating unit having a lactone group, a sultone group or a carbonate group is preferably 1 to 50 mol % based on all the repeating units in the specific resin X, more preferably 5 to 60 mol %, and even more preferably 5 to 50 mol %.

[0372] <Repeating unit having an acid group>

[0373] The specific resin X may include a repeating unit having an acid group.

[0374] As the acid group, an acid group having a pKa of 13 or less is preferred.

[0375] As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferable.

[0376] Furthermore, in the above-mentioned hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted by groups other than fluorine atoms (such as alkoxycarbonyl groups). The -C(CF3)(OH)-CF2- formed in this way is also preferably used as an acid group. Furthermore, one or more fluorine atoms may be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0377] The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected by a leaving group that leaves by the action of the acid and the repeating unit having a lactone group, a sultone group or a carbonate group.

[0378] The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0379] As the repeating unit having an acid group, a repeating unit represented by formula (B) is preferred.

[0380] [Chemical formula 20]

[0381]

[0382] R3 represents a hydrogen atom or a monovalent substituent which may have a fluorine atom or an iodine atom.

[0383] As a monovalent substituent which may have a fluorine atom or an iodine atom, a group represented by -L4-R8 is preferred. L4 represents a single bond or an ester group. R8 may include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group formed by combining these.

[0384] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

[0385] L2 represents a single bond or an ester group.

[0386] L3 represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. Examples of the alicyclic hydrocarbon ring group include a monocyclic ring or a polycyclic ring, and examples thereof include a cycloalkyl ring group.

[0387] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). When R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon ring group having a valence of (n+m+1).

[0388] R7 represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0389] m represents an integer greater than or equal to 1. m is preferably an integer of 1-3, and more preferably an integer of 1-2.

[0390] n represents an integer greater than or equal to 0 or 1. n is preferably an integer of 0-4.

[0391] In addition, (n+m+1) is preferably an integer of 1-5.

[0392] The repeating unit having an acid group may be a repeating unit composed of (meth)acrylic acid.

[0393] As the repeating unit having an acid group, for example, the repeating units described in paragraphs

[0050] to

[0075] of JP-A-2014-010245 can also be used, and the contents thereof are incorporated into the present specification.

[0394] The content of the repeating unit having an acid group is preferably 10 to 60 mol % based on all the repeating units in the specific resin X, more preferably 10 to 50 mol %, and even more preferably 10 to 40 mol %.

[0395] <Repeating unit having a hydroxyl group>

[0396] The specific resin X may contain a repeating unit having a hydroxyl group. This improves substrate adhesion and developer affinity.

[0397] The repeating unit having a hydroxyl group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group.

[0398] It is preferred that the repeating unit having a hydroxyl group has no acid-decomposable group.

[0399] The hydroxyl group in the repeating unit having a hydroxyl group is preferably not a hydroxyl group constituting an acid group.

[0400] Examples of the repeating unit having a hydroxyl group include repeating units represented by the following general formulae (AIIa) to (AIId).

[0401] [Chemical formula 21]

[0402]

[0403] In the general formula (AIIa) to the general formula (AIId),

[0404] R 1crepresents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0405] R 2c ~R 4c Each independently represents a hydrogen atom or a hydroxyl group. 2c ~R 4c At least one of them represents a hydroxyl group. 2c ~R 4c One or two of them are hydroxyl groups, and the rest are hydrogen atoms. 2c ~R 4c Two of them are hydroxyl groups and the rest are hydrogen atoms.

[0406] As the repeating unit having a hydroxyl group, for example, the repeating units described in paragraphs

[0133] to

[0142] of JP-A-2014-010245 can also be used, and these contents are incorporated into the present specification.

[0407] The content of the repeating unit having a hydroxyl group is preferably 5 to 60 mol % based on all the repeating units in the specific resin X, more preferably 5 to 50 mol %, and even more preferably 5 to 40 mol %.

[0408] <Repeating unit for reducing the mobility of the main chain>

[0409] From the viewpoint of being able to suppress excessive diffusion of the generated acid or pattern collapse during development, the specific resin X preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, too high Tg leads to a decrease in the dissolution rate in the developer, so Tg is preferably 400°C or less, more preferably 350°C or less.

[0410] In order to increase the Tg of the specific resin X, it is preferable to reduce the mobility of the main chain of the specific resin X. As a method of reducing the mobility of the main chain of the specific resin X, a method of connecting a cyclic structure to the main chain is mentioned.

[0411] Repeating unit represented by formula (E)

[0412] As an example of a method for connecting a cyclic structure to the main chain, a method of introducing a repeating unit represented by formula (E) into the specific resin X can be mentioned.

[0413] [Chemical formula 22]

[0414]

[0415] In formula (E), Re each independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group which may have a substituent.

[0416] "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited.

[0417] Specific examples of the repeating unit represented by formula (E) include the following repeating units.

[0418] [Chemical formula 23]

[0419]

[0420] [Chemical formula 24]

[0421]

[0422] In the above formula, R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above alkyl group, the above cycloalkyl group, the above aryl group, the above aralkyl group and the above alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R may be substituted by a fluorine atom or an iodine atom.

[0423] R' independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR" or -COOR": R" is an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms) or a carboxyl group. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryl group, the above-mentioned aralkyl group and the above-mentioned alkenyl group may each have a substituent. Furthermore, a hydrogen atom bonded to a carbon atom in the group represented by R' may be substituted by a fluorine atom or an iodine atom.

[0424] m represents an integer greater than or equal to 0. The upper limit of m is not particularly limited, but is often less than or equal to 2, and more often less than or equal to 1.

[0425] Furthermore, two Rs bonded to the same carbon atom may bond to each other to form a ring.

[0426] In formula (E-2), formula (E-4), formula (E-6) and formula (E-8), two Rs may form "=O" together.

[0427] The content of the repeating unit represented by the formula (E) is preferably 5 to 60 mol % based on all the repeating units in the specific resin X, and more preferably 10 to 55 mol %.

[0428] The method of increasing the Tg of the specific resin X is not limited to others, and the method of introducing a repeating unit described in paragraphs

[0105] to

[0128] of JP-A-2019-045864 may also be mentioned.

[0429] In addition to the above-mentioned repeating structural units, the specific resin X may have various repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0430] As the specific resin X, (especially when the resist composition is used as an ArF photosensitive ray or radiation-sensitive resin composition) it is also preferred that all repeating units are composed of (meth)acrylate repeating units. In this case, any one of the following repeating units can be used, that is, a repeating unit in which all repeating units are methacrylate repeating units, a repeating unit in which all repeating units are acrylate repeating units, and a repeating unit in which all repeating units are composed of methacrylate repeating units and acrylate repeating units. The acrylate repeating unit is preferably 50 mol% or less of all repeating units.

[0431] [Specific resin Y (second embodiment)]

[0432] <Acid-decomposable group>

[0433] The specific resin Y contains a group (acid-decomposable group) that is decomposed by the action of an acid to increase polarity, and preferably contains a repeating unit having an acid-decomposable group.

[0434] The "acid-decomposable group" and "repeating unit having an acid-decomposable group" possessed by the specific resin Y have the same meanings as the "acid-decomposable group" and "repeating unit having an acid-decomposable group" that the above-mentioned specific resin X may have, and preferred embodiments thereof are also the same.

[0435] When the specific resin Y contains a repeating unit having an acid-decomposable group, the content of the repeating unit having an acid-decomposable group relative to all repeating units in the specific resin Y is preferably 15 to 95 mol %, more preferably 30 to 80 mol %, and even more preferably 30 to 70 mol %.

[0436] <Groups containing the first structural part and groups containing the second structural part>

[0437] The group containing the first structural part and the group containing the second structural part correspond to the group containing the specific structural part contained in the above-mentioned specific compound. The structure of the group containing the first structural part and the group containing the second structural part is not limited as long as they contain the above-mentioned specific structural part.

[0438] As the group containing the first structural site and the group containing the second structural site, a group containing a site represented by the above-mentioned general formula (D1) or general formula (D2) is preferred.

[0439] The group containing the first structural part and the group containing the second structural part can be included in the specific resin Y in any form. For example, in the specific resin Y, the group containing the first structural part and the group containing the second structural part can be bonded to the end of the main chain. In addition, the specific resin Y can contain a repeating unit containing a group containing the first structural part and a repeating unit containing a group containing the second structural part, respectively. In addition, the specific resin Y can contain a repeating unit containing a group containing the first structural part and a group containing the second structural part. When the specific resin Y is suitable for use in an anti-etching composition, it is preferred to contain a repeating unit containing a group containing the first structural part and a group containing the second structural part in terms of better LWR performance of the formed pattern.

[0440] In the specific resin Y, the second acidic site derived from the second anionic site in the group containing the second structural site has a structure different from the first acidic site derived from the first anionic site in the group containing the first structural site, and has an acid dissociation constant greater than that of the first acidic site.

[0441] The acid dissociation constant was determined by the above method.

[0442] In addition, in the case where the specific resin Y contains a repeating unit including a group containing a first structural part and a repeating unit including a group containing a second structural part, and in the case where it contains a repeating unit including a group containing a first structural part and a group containing a second structural part, the acid dissociation constant of the first acidic part and the acid dissociation constant of the second acidic part in the specific resin Y are calculated based on the monomers constituting each repeating unit.

[0443] Specifically, when the specific resin Y has a structure containing a repeating unit containing a group containing a first structural part and a repeating unit containing a group containing a second structural part, respectively, the acid dissociation constant is determined by the above-mentioned method with respect to each of a compound in which the cation part of a monomer constituting the repeating unit containing a group containing a first structural part is substituted with a hydrogen atom and a compound in which the cation part of a monomer constituting the repeating unit containing a group containing a second structural part is substituted with a hydrogen atom.

[0444] Furthermore, when the specific resin Y has a structure containing a repeating unit including a group containing a first structural part and a group containing a second structural part, the acid dissociation constant is determined by the above method with respect to a compound in which the cationic part of a monomer constituting the repeating unit is substituted with a hydrogen atom. In this case, a two-step dissociation constant can be obtained.

[0445] In the specific resin Y, the preferred numerical range of the acid dissociation constant of the first acidic site is the same as the acid dissociation constant a1 of the above-mentioned compound PI (corresponding to the acid generated by irradiating compound (I) with actinic rays or radiation). Furthermore, the preferred numerical range of the acid dissociation constant of the second acidic site is the same as the acid dissociation constant a2 of the above-mentioned compound PI. Furthermore, the preferred numerical range of the difference between the acid dissociation constant of the first acidic site and the acid dissociation constant of the second acidic site is the same as the difference between the acid dissociation constant a1 and the acid dissociation constant a2 in the above-mentioned compound PI.

[0446] As a method for making the acid dissociation constant of the second acidic site larger than the acid dissociation constant of the first acidic site, there is a method of making the first anion site and the second anion site in the specific resin Y have different structures from each other.

[0447] As a combination of the first anion part (anionic functional group) and the second anion part (anionic functional group), for example, a combination of the above-mentioned general formula (B-10) and the above-mentioned general formula (C-1), a combination of the above-mentioned general formula (B-10) and the above-mentioned general formula (C-8), a combination of the above-mentioned general formula (C-1) and the above-mentioned general formula (B-8), a combination of the above-mentioned general formula (C-1) and the above-mentioned general formula (B-1) or a combination of the above-mentioned general formula (B-2) and the above-mentioned general formula (B-6).

[0448] When the specific resin Y contains a repeating unit including a group containing a first structural part and a group containing a second structural part, the content of the repeating unit is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more, relative to all repeating units in the specific resin Y. The upper limit is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 15 mol% or less.

[0449] In addition, when the specific resin Y contains a repeating unit containing a group containing a first structural part and a repeating unit containing a group containing a second structural part, the total content of the repeating unit containing the group containing the first structural part and the repeating unit containing the group containing the second structural part relative to all repeating units in the specific resin Y is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more. And, as its upper limit, it is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 15 mol% or less. The content ratio (molar ratio) of the repeating unit containing the group containing the first structural part and the repeating unit containing the group containing the second structural part is preferably 30 / 70 to 70 / 30.

[0450] <Repeating unit having a lactone group, a sultone group or a carbonate group>

[0451] The specific resin Y may contain a repeating unit having a lactone group, a sultone group or a carbonate group.

[0452] The "repeating unit having a lactone group, a sultone group or a carbonate group" possessed by the specific resin Y has the same meaning as the "repeating unit having a lactone group, a sultone group or a carbonate group" that the above-mentioned specific resin X may have, and its preferred embodiment (including the content) is also the same.

[0453] <Repeating unit having an acid group>

[0454] The specific resin Y may include a repeating unit having an acid group.

[0455] The “repeating unit having an acid group” of the specific resin Y has the same meaning as the “repeating unit having an acid group” that the specific resin X may have, and preferred embodiments thereof (including the content) are also the same.

[0456] <Repeating unit having a hydroxyl group>

[0457] The specific resin Y may include a repeating unit having a hydroxyl group.

[0458] The “repeating unit having a hydroxyl group” of the specific resin Y has the same meaning as the “repeating unit having a hydroxyl group” which the specific resin X may have, and preferred embodiments thereof (including the content) are also the same.

[0459] <Repeating unit for reducing the mobility of the main chain>

[0460] The specific resin Y may have a repeating unit for reducing the mobility of the main chain.

[0461] The "repeating unit for reducing the mobility of the main chain" possessed by the specific resin Y has the same meaning as the "repeating unit for reducing the mobility of the main chain" that the above-mentioned specific resin X may have, and its preferred embodiment (including the content) is also the same.

[0462] In addition to the above-mentioned repeating structural units, the specific resin Y may have various repeating structural units for the purpose of adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0463] As the specific resin Y, (especially when the resist composition is used as an ArF photosensitive ray or radiation-sensitive resin composition) it is also preferred that all repeating units are composed of (meth)acrylate repeating units. In this case, any one of the following repeating units can be used, that is, a repeating unit in which all repeating units are methacrylate repeating units, a repeating unit in which all repeating units are acrylate repeating units, and a repeating unit in which all repeating units are composed of methacrylate repeating units and acrylate repeating units. The acrylate repeating unit is preferably 50 mol% or less of all repeating units.

[0464] [Physical properties of specific resin X and specific resin Y]

[0465] The specific resin X and the specific resin Y can be synthesized by a conventional method (for example, radical polymerization).

[0466] The weight average molecular weight of the specific resin X and the specific resin Y is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000 as a polystyrene conversion value based on the GPC method. By setting the weight average molecular weight of the specific resin X and the specific resin Y to 1,000 to 200,000, it is possible to further suppress the deterioration of heat resistance and dry etching resistance. In addition, it is possible to further suppress the deterioration of film forming properties due to deterioration of developability and increased viscosity.

[0467] The dispersity (molecular weight distribution) of the specific resin X and the specific resin Y is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

[0468] [Acticular ray-sensitive or radiation-sensitive resin composition]

[0469] The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as a "resist composition") of the present invention will be described.

[0470] The resist composition of the present invention contains the specific resin X or the specific resin Y described above.

[0471] The resist composition of the present invention may be a positive resist composition or a negative resist composition, and may be a resist composition for alkaline development or a resist composition for organic solvent development.

[0472] The resist composition of the present invention is typically a chemically amplified resist composition.

[0473] Hereinafter, components that may be contained in the resist composition will be described in detail.

[0474] [Specific resin X and specific resin Y]

[0475] The resist composition of the present invention contains a specific resin X or a specific resin Y. The specific resin X and the specific resin Y are as described above.

[0476] In the resist composition of the present invention, the content of the specific resin X and the specific resin Y (the total content when a plurality of specific resins are included) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.

[0477] In addition, the solid content means the components other than the solvent in the composition, and any component other than the solvent, even if it is a liquid component, is regarded as a solid content.

[0478] Furthermore, the specific resin X and the specific resin Y may be used alone or in combination of two or more.

[0479] When the resist composition of the present invention contains a specific resin X and the specific resin X is a resin having no acid-decomposable group, it is preferred that the resist composition of the present invention contains a resin having an acid-decomposable group (preferably a resin containing a repeating unit having an acid-decomposable group) separately from the specific resin X. The resin having an acid-decomposable group is not particularly limited, and examples thereof include known resins.

[0480] 〔Photoacid generator〕

[0481] The resist composition may contain a photoacid generator (a compound that generates an acid by irradiation with actinic rays or radiation other than the specific resin X and the specific resin Y) other than the specific resin X and the specific resin Y. Other photoacid generators are compounds that generate an acid by exposure (preferably exposure to EUV light and / or ArF).

[0482] The other photoacid generator may be in the form of a low molecular weight compound or in the form of being embedded in a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being embedded in a part of a polymer may be used in combination.

[0483] When the other photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.

[0484] When the other photoacid generator is in a form embedded in a part of a polymer, it is preferably embedded in a resin different from the specific resin X and the specific resin Y.

[0485] In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound.

[0486] The other photoacid generators are not particularly limited, but are preferably compounds that generate organic acids. Examples of the organic acid include those described as organic acids that can be generated by the specific compound.

[0487] Examples of other photoacid generators include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, azodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

[0488] Other photoacid generators may be zwitterions.

[0489] As other photoacid generators, known compounds that generate acid by irradiation with activating light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0086] to

[0094] of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs

[0323] to

[0402] of U.S. Patent Application Publication No. 2016 / 0237190A1 can be used.

[0490] When the resist composition contains other photoacid generators, the content thereof is not particularly limited, but is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.5 to 10% by mass based on the total solid content of the composition in terms of more excellent effects of the present invention.

[0491] The other photoacid generators may be used alone or in combination of two or more.

[0492] 〔Solvent〕

[0493] The resist composition may contain a solvent.

[0494] The solvent preferably contains at least one selected from (M1) propylene glycol monoalkyl ether carboxylates (propylene glycol monomethyl ether acetate (PGMEA) and the like), (M2) propylene glycol monoalkyl ethers (propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE) and the like), lactates (ethyl lactate and the like), acetates, alkoxypropionates, linear ketones, cyclic ketones (2-heptanone, cyclohexanone or cyclopentanone and the like), lactones (γ-butyrolactone and the like), and alkylene carbonates (propylene carbonate and the like). In addition, the solvent may contain components other than components (M1) and (M2).

[0495] The solvent preferably contains component (M1). More preferably, the solvent is substantially composed of component (M1) alone or is a mixed solvent of component (M1) and other components. In the latter case, the solvent further preferably contains both component (M1) and component (M2).

[0496] The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably "100 / 0" to "0 / 100", more preferably "100 / 0" to "15 / 85", further preferably "100 / 0" to "40 / 60", and particularly preferably "100 / 0" to "60 / 40".

[0497] As described above, the solvent may contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.

[0498] The content of the solvent in the resist composition is preferably set to a solid content concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. This can further improve the coating properties of the resist composition.

[0499] In addition, the solid content means all components except the solvent.

[0500] 〔Acid diffusion control agent〕

[0501] The resist composition may further contain an acid diffusion controller. The acid diffusion controller functions as a quencher that captures the acid generated by the photoacid generator and functions to control the diffusion phenomenon of the acid in the resist film.

[0502] The acid diffusion controller may be, for example, a basic compound.

[0503] The basic compound is preferably a compound having a structure represented by the following general formula (A) to general formula (E).

[0504] [Chemical formula 25]

[0505]

[0506] In the general formula (A) and the general formula (E), R 200 , R 201 and R 202 may be the same or different, and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Here, R 201 and R 202 They may be bonded to each other to form a ring.

[0507] As for the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[0508] R 203 , R 204 , R 205 and R 206 The groups may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

[0509] The alkyl groups in the general formula (A) and the general formula (E) are more preferably unsubstituted.

[0510] (Produces a compound having a proton accepting functional group, and decomposes by irradiation with actinic rays or radiation, thereby reducing or eliminating the proton accepting property, or changing from proton accepting property to acidic property (PA))

[0511] The resist composition may contain, as an acid diffusion controller, a compound that generates a compound having a proton accepting functional group and decomposes by irradiation with actinic rays or radiation to reduce or eliminate the proton accepting property or to change from proton accepting property to acidic property (hereinafter also referred to as compound (PA)).

[0512] The proton accepting functional group is a functional group having a group or electron that can electrostatically interact with a proton, and for example, it refers to a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

[0513] [Chemical formula 26]

[0514]

[0515] Preferred partial structures of the proton accepting functional group include, for example, a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

[0516] Compound (PA) generates a compound that is decomposed by irradiation with actinic rays or radiation, thereby reducing or eliminating proton accepting properties or changing from proton accepting properties to acidic properties. Here, the reduction or disappearance of proton accepting properties or the change from proton accepting properties to acidic properties is a change in proton accepting properties caused by the addition of protons to proton accepting functional groups. Specifically, it means that when a proton adduct is generated from a compound (PA) having a proton accepting functional group and a proton, the equilibrium constant of the chemical equilibrium decreases.

[0517] As compound (PA), for example, compounds described in paragraphs

[0421] to

[0428] of JP-A-2014-41328 and paragraphs

[0108] to

[0116] of JP-A-2014-134686 can be cited, and the contents thereof are incorporated into the present specification.

[0518] A low molecular weight compound having a nitrogen atom and a group that is dissociated by the action of an acid can also be used as the acid diffusion controller. The low molecular weight compound is preferably an amine derivative having a group that is dissociated by the action of an acid on the nitrogen atom.

[0519] The group that is released by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiamalin ether group, and more preferably a carbamate group or a hemiamalin ether group.

[0520] The molecular weight of the low molecular weight compound is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0521] The low molecular weight compound may have a carbamate group having a protecting group on the nitrogen atom.

[0522] Examples of the acid diffusion controller include compounds described in paragraphs

[0140] to

[0144] of JP-A-2013-11833 (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like).

[0523] As the acid diffusion controller, for example, the contents described in paragraphs

[0123] to

[0159] of JP-A-2018-155788 can also be cited.

[0524] Specific examples of the acid diffusion controller are shown below, but the present invention is not limited thereto.

[0525] [Chemical formula 27]

[0526]

[0527] [Chemical formula 28]

[0528]

[0529] When the resist composition contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.001 to 15% by mass, more preferably 0.01 to 8% by mass, based on the total solid content of the resist composition.

[0530] The acid diffusion controller may be used alone or in combination of two or more.

[0531] 〔Hydrophobic resin〕

[0532] The resist composition may contain a hydrophobic resin different from the specific resin X and the specific resin Y separately from the specific resin X and the specific resin Y described above.

[0533] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and does not need to contribute to uniform mixing of polar and nonpolar substances.

[0534] Examples of the effects of adding a hydrophobic resin include control of static and dynamic contact angles of the resist film surface with respect to water and suppression of outgassing.

[0535] From the viewpoint of partial localization to the film surface, the hydrophobic resin preferably has any one or more of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain part of the resin", and more preferably has two or more. In addition, the hydrophobic resin preferably has a hydrocarbon group with a carbon number of 5 or more. These groups may be present in the main chain of the resin or may be substituted by a side chain.

[0536] Regarding the hydrophobic resin, reference can be made to the description in paragraphs

[0315] to

[0415] of JP-A-2014-010245, and these contents are incorporated into the specification of the present application.

[0537] In addition, as the hydrophobic resin, resins described in Japanese Patent Application Laid-Open Nos. 2011-248019, 2010-175859, and 2012-032544 can also be preferably used.

[0538] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resist composition.

[0539] 〔Surfactant〕

[0540] The resist composition may contain a surfactant. If the resist composition contains a surfactant, a pattern with more excellent adhesion and fewer development defects can be formed.

[0541] The surfactant is preferably a fluorine-based and / or silicon-based surfactant.

[0542] Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph

[0276] of US Patent Application Publication No. 2008 / 0248425. In addition, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 and 4430 (manufactured by Sumitomo 3M Limited); Megaface F171, F173, F176, F189, F113, F110, F177, F120 and R08 (manufactured by DIC CORPORATION); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by SEIMI CHEMICAL CO., LTD. manufacturing); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA Solutions Inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (manufactured by Neos Corporation). In addition, as a silicon-based surfactant, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0543] In addition, the surfactant can be synthesized by using a fluoroaliphatic compound manufactured by a telomerization method (also called a short-chain polymer (telomer) method) or an oligomerization method (also called an oligomer method) in addition to the known surfactants shown above. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound can be used as a surfactant. The fluoroaliphatic compound can be synthesized by the method described in, for example, Japanese Patent Application Laid-Open No. 2002-90991.

[0544] Furthermore, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph

[0280] of the specification of US Patent Application Publication No. 2008 / 0248425 may also be used.

[0545] These surfactants may be used alone or in combination of two or more.

[0546] When the resist composition contains a surfactant, the content of the surfactant is preferably 0.0001 to 2 mass %, more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

[0547] 〔Other additives〕

[0548] The resist composition may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber and / or a compound promoting solubility in a developer (eg, a phenol compound having a molecular weight of 1000 or less or an alicyclic or aliphatic compound containing a carboxylic acid group).

[0549] [Resist film, pattern forming method]

[0550] The procedure of the pattern forming method using the above-mentioned resist composition is not particularly limited, but preferably includes the following steps.

[0551] Step 1: Step of forming a resist film on a substrate using a resist composition

[0552] Step 2: Exposure of the resist film

[0553] Step 3: Step of developing the exposed resist film using a developer to form a pattern

[0554] Hereinafter, the steps of each of the above processes will be described in detail.

[0555] [Step 1: Resist film forming step]

[0556] Step 1 is a step of forming a resist film on a substrate using a resist composition.

[0557] The resist composition is as defined above.

[0558] A specific example of the method for preparing the resist composition is shown below.

[0559] In the resist composition used in the pattern forming method of the present invention, the content of metal atoms is preferably reduced.

[0560] Hereinafter, first, a specific example of a method for reducing the metal atom content in a resist composition is described, and then a specific example of a method for preparing the resist composition is described.

[0561] As a method for reducing the content of metal atoms in the resist composition, for example, a regulation method by filtering using a filter can be cited. As the filter pore size, the pore size is preferably less than 100nm, more preferably less than 10nm, and further preferably less than 5nm. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can be composed of a composite material combining the above-mentioned filter raw materials and ion exchange media. The filter can use a filter pre-cleaned with an organic solvent. In the filter filtering process, a variety of filters can be connected in series or in parallel and used. When using a variety of filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can be a circulating filtration process.

[0562] In addition, as a method for reducing the metal atom content in the resist composition, there can be cited a method of selecting a raw material with a low metal content as a raw material for each material constituting the resist composition, a method of filtering the raw materials for each material constituting the resist composition, and a method of performing distillation under conditions that minimize contamination by lining the inside of an apparatus with Teflon (registered trademark), etc.

[0563] Furthermore, as a method for reducing the metal atom content in the resist composition, in addition to the above-mentioned filtration, it can also be removed by an adsorbent, or a combination of filtration and adsorbent can be used. As the adsorbent, a known adsorbent can be used, for example, an inorganic adsorbent such as silica gel and zeolite and an organic adsorbent such as activated carbon can be used.

[0564] Furthermore, in order to reduce the metal atom content in the resist composition, it is necessary to prevent the mixing of metal impurities during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing device can be confirmed by measuring the content of the metal component contained in the cleaning solution used when cleaning the manufacturing device.

[0565] Next, a specific example of the method for preparing the resist composition will be described.

[0566] In the manufacture of the resist composition, for example, it is preferred to dissolve various components such as the above-mentioned resin and the photoacid generator in a solvent, and then use multiple filters with different raw materials to filter (it can also be a circulation filtration). For example, it is preferred that a polyethylene filter with a pore size of 50nm, a nylon filter with a pore size of 10nm, and a polyethylene filter with a pore size of 3 to 5nm are connected in sequence for filtration. The filtration is also preferably carried out by a circulation filtration method more than 2 times. In addition, the above-mentioned filtration process also has the effect of reducing the metal atom content in the resist composition. The pressure difference between the filters is as small as possible, usually 0.1MPa or less, preferably 0.05MPa or less, and more preferably 0.01MPa or less. The pressure difference between the filter and the filling nozzle is also as small as possible, usually 0.5MPa or less, preferably 0.2MPa or less, and more preferably 0.1MPa or less.

[0567] In addition, as a method of performing circulation filtration using a filter in the production of the resist composition, a method of performing circulation filtration two or more times using a polytetrafluoroethylene filter having a pore size of 50 nm is also preferred.

[0568] It is preferred to replace the gas inside the resist composition production apparatus with an inert gas such as nitrogen, thereby suppressing the dissolution of active gases such as oxygen into the resist composition.

[0569] After the resist composition is filtered through a filter, it is filled in a clean container. The resist composition filled in the container is preferably refrigerated. Thus, the performance degradation caused by the passage of time is suppressed. The shorter the time from the end of filling the resist composition into the container to the start of refrigerated storage, the better, usually within 24 hours, preferably within 16 hours, more preferably within 12 hours, and more preferably within 10 hours. The storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and more preferably 0 to 5°C.

[0570] Next, a method for forming a resist film on a substrate using the resist composition will be described.

[0571] As a method of forming a resist film on a substrate using a resist composition, a method of applying the resist composition on a substrate is mentioned, for example.

[0572] The resist composition can be applied to a substrate (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit elements by an appropriate coating method such as a spin coater or a coating machine. The coating method is preferably spin coating using a spin coater. The rotation speed when spin coating using a spin coater is preferably 1000 to 3000 rpm.

[0573] After the resist composition is applied, the substrate may be dried to form a resist film. In addition, various base films (inorganic film, organic film, anti-reflection film) may be formed under the resist film as needed.

[0574] As a drying method, for example, a method of drying by heating can be cited. Heating can be performed using a device provided in a general exposure machine and / or a developer, or can be performed using a hot plate or the like. The heating temperature is preferably 80 to 150° C., more preferably 80 to 140° C., and further preferably 80 to 130° C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and further preferably 60 to 600 seconds.

[0575] The film thickness of the resist film is not particularly limited, but is preferably 10 to 90 nm, more preferably 10 to 65 nm, and even more preferably 15 to 50 nm from the viewpoint of being able to form a finer pattern with higher precision.

[0576] Alternatively, a top coat layer may be formed on the resist film using a top coat composition.

[0577] It is preferred that the top coating composition can be further uniformly applied to the upper layer of the resist film without being mixed with the resist film.

[0578] The top coating composition includes, for example, a resin, an additive, and a solvent.

[0579] The top coat layer is not particularly limited, and a conventionally known top coat layer can be formed by a conventionally known method. For example, the top coat layer can be formed based on the contents described in paragraphs

[0072] to

[0082] of Japanese Patent Application Laid-Open No. 2014-059543.

[0580] For example, it is preferable to form a top coat layer containing a basic compound as described in Japanese Patent Application Laid-Open No. 2013-61648 on the resist film. Specific examples of the basic compound that can be contained in the top coat layer include basic compounds that can be contained in the resist composition.

[0581] Furthermore, the top coating layer preferably further includes a compound including at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0582] [Process 2: Exposure process]

[0583] Step 2 is a step of exposing the resist film to light.

[0584] As an exposure method, a method of irradiating the formed resist film with light through a predetermined mask is mentioned, for example.

[0585] After exposure, it is preferred to perform baking (heating) before development. Baking promotes the reaction of the exposed portion, and the sensitivity and pattern shape become better.

[0586] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C.

[0587] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[0588] Heating can be performed using a device included in a general exposure machine and / or a developing machine, or heating can be performed using a hot plate or the like.

[0589] This process is also called post-exposure bake.

[0590] [Process 3: Development process]

[0591] Step 3 is a step of developing the exposed resist film using a developer to form a pattern.

[0592] The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0593] As developing methods, for example, there can be cited: a method of immersing a substrate in a tank filled with a developer for a certain period of time (dip method); a method of developing by causing the developer to bulge on the surface of the substrate due to surface tension and allowing the developer to stand for a certain period of time (puddle method); a method of spraying the developer onto the surface of the substrate (spray method); and a method of continuously spraying the developer on a substrate rotating at a certain speed while scanning a developer spray nozzle at a certain speed (dynamic dispense method).

[0594] Furthermore, after the step of developing, a step of stopping the development while replacing the solvent with another solvent may be performed.

[0595] The development time is not particularly limited as long as it is a time for the resin in the unexposed portion to fully dissolve, but is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.

[0596] The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0597] The alkaline developer preferably uses an alkaline aqueous solution containing an alkali. The type of the alkaline aqueous solution is not particularly limited, and examples thereof include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines or cyclic amines. Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. may be added to the alkaline developer. The alkali concentration of the alkaline developer is generally 0.1 to 20% by mass. In addition, the pH of the alkaline developer is generally 10.0 to 15.0.

[0598] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0599] The developer may contain a plurality of solvents or other solvents or water. The developer may contain water in an amount of less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass. The developer may contain substantially no water.

[0600] The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, relative to the total amount of the developer.

[0601] 〔Other processes〕

[0602] The above-mentioned pattern forming method preferably includes a step of cleaning with a rinse liquid after step 3.

[0603] As a rinse liquid used in the rinse step after the step of developing with an alkaline developer, pure water can be mentioned, for example. In addition, an appropriate amount of a surfactant can be added to the pure water.

[0604] An appropriate amount of surfactant may be added to the flushing solution.

[0605] The rinse solution used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse solution preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0606] The method of the rinsing step is not particularly limited. Examples include a method of continuously spraying a rinsing liquid onto a substrate rotating at a certain speed (spin coating method), a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time (immersion method), and a method of spraying the rinsing liquid onto the surface of the substrate (spray coating method).

[0607] Furthermore, the pattern forming method of the present invention may include a heating process (Post Bake) after the rinsing process. This process can remove the developer and rinse solution remaining between and inside the patterns due to baking. Furthermore, this process also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0608] Then, the formed pattern can be used as a mask to perform etching processing on the substrate.

[0609] Any known method can be used for etching, and various conditions are appropriately determined according to the type or purpose of the substrate. For example, etching can be performed according to the Proc. of SPIE Vol. 6924, 692420 (2008), Japanese Patent Publication No. 2009-267112, etc. In addition, etching can be performed according to the method described in "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition 2007 Issued by SEMI Japan".

[0610] In various materials other than the resist composition used in the pattern forming method of the present invention (e.g., developer, rinse solution, antireflective film forming composition, topcoat layer forming composition, etc.), the less impurities such as metals (e.g., Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn, etc.), the better. The content of impurities contained in these materials is, for example, preferably 1 mass ppm or less.

[0611] As a method for reducing impurities such as metals in various materials other than the resist composition, for example, filtration using a filter can be cited. As the filter pore size, the pore size is preferably less than 100nm, more preferably less than 10nm, and further preferably less than 5nm. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can be composed of a composite material combining the above-mentioned filter raw materials and an ion exchange medium. The filter can use a filter pre-cleaned with an organic solvent. In the filter filtering process, a variety of filters can be connected in series or in parallel and used. When using a variety of filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can be a circulating filtration process.

[0612] Furthermore, methods for reducing impurities such as metals in various materials other than the resist composition include a method of selecting raw materials with a low metal content as raw materials constituting various materials, a method of filtering the raw materials constituting various materials, and a method of performing distillation under conditions that minimize contamination by lining the inside of an apparatus with Teflon (registered trademark), etc.

[0613] In addition, as a method for reducing impurities such as metals in various materials other than the resist composition, in addition to the above-mentioned filter filtration, impurities can also be removed by an adsorbent, or a combination of filter filtration and adsorbent can be used. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in various materials other than the above-mentioned resist composition, it is necessary to prevent the mixing of metal impurities in the manufacturing process. It is possible to confirm whether the metal impurities are fully removed from the manufacturing device by measuring the content of the metal component contained in the cleaning solution used when cleaning the manufacturing device.

[0614] In order to prevent the failure of the liquid piping and various components (filters, O-rings, hoses, etc.) caused by static electricity charging and subsequent static electricity discharge, a conductive compound can be added to the organic treatment liquid such as the rinse liquid. The conductive compound is not particularly limited, and methanol can be cited as an example. The amount added is not particularly limited, and from the viewpoint of maintaining the preferred development characteristics or rinse characteristics, it is preferably 10% by mass or less, and more preferably 5% by mass or less.

[0615] As the liquid medicine piping, SUS (stainless steel) or various pipings coated with polyethylene, polypropylene or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used. Similarly, polyethylene, polypropylene or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

[0616] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method and an electronic device manufactured by the manufacturing method.

[0617] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).

[0618] Example

[0619] Below, the present invention is further described in detail according to the embodiments. As long as it does not depart from the purpose of the present invention, the material, usage, ratio, processing content and processing steps shown in the following embodiments can be appropriately changed. Therefore, the scope of the present invention should not be interpreted as being limited by the following embodiments.

[0620] [Various ingredients]

[0621] 〔Resin〕

[0622] Resins A-1 to A-13 shown in Tables 4 and 8 were synthesized according to the synthesis method of resin A-5 described later (Synthesis Example 1). Table 1 shows the composition ratio (molar ratio; corresponding from left to right), weight average molecular weight (Mw) and dispersion degree (Mw / Mn) of each repeating unit described later.

[0623] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) (in terms of polystyrene) of the resins A-1 to A-13 were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (mol %) of the resin was measured by C-NMR (nuclear magnetic resonance).

[0624] [Table 1]

[0625]

[0626] The structural formulas of resins A-1 to A-13 shown in Table 1 are shown below.

[0627] [Chemical formula 29]

[0628]

[0629] [Chemical formula 30]

[0630]

[0631]

[0632] <Synthesis Example 1: Synthesis of Resin A-5>

[0633] (Synthesis Example 1A: Synthesis of Compound (1))

[0634] [Chemical formula 31]

[0635]

[0636] 《Synthesis of Compound (1-1)》

[0637] 30.0 g of trifluoromethanesulfonamide was dissolved in 90 g of dehydrated THF and cooled to 0°C. After adding 65.0 g of diisopropylethylamine (DIPEA) at 0°C, a solution of 63.3 g of compound (A) dissolved in 30 g of dehydrated THF was added dropwise using a dropping funnel. After that, the mixture was stirred at 25°C for 1 hour, and 400 ml of 1N hydrochloric acid was added dropwise to the reaction system. Dichloromethane was added to the organic layer, and the mixture was washed three times with 150 g of water. The concentrated solution was subjected to column chromatography to obtain 84.0 g of compound (1-1).

[0638] 《Synthesis of Compound (1-2)》

[0639] 84.0 g of compound (1-1) was dissolved in 250 g of THF, and ammonia gas was introduced at 0°C. After 2 hours, the mixture was added dropwise to 1000 ml of 1N hydrochloric acid, and dichloromethane was added, followed by washing with 300 g of water three times. The obtained organic layer was concentrated to obtain 54.0 g of compound (1-2).

[0640] 《Synthesis of Compound (1-3)》

[0641] 17.0 g of compound (1-2) was dissolved in 100 g of dichloromethane and cooled to 0°C. After adding 9.61 g of diisopropylethylamine at 0°C, a solution of 7.42 g of compound (B) dissolved in 19 g of dichloromethane (DCM) was added dropwise using a dropping funnel. After that, the mixture was stirred at 0°C for 1 hour, and the reaction solution was washed three times with 100 g of water. The concentrated solution was subjected to column chromatography to obtain 21.0 g of compound (1-3).

[0642] 《Synthesis of Compound (1)》

[0643] 21.0 g of compound (1-3) was dissolved in 170 g of dichloromethane, 150 g of pure water was added, and 8.09 g of compound (C) was further added. The mixture was stirred at 25°C for 1 hour, and the reaction solution was washed five times with 100 g of water. The concentrated solution was subjected to column chromatography to obtain 14.0 g of compound (1).

[0644] Compound (1): 1 H-NMR (CDCl3) δppm 7.77-7.61 (30H, m), 6.07 (1H, s), 5.51 (1H, s), 4.21 (2H, t), 3.24 (2H, q), 2.23 (2H, m), 1.89 (3H, s)

[0645] <Synthesis Example 2: Synthesis of Resin A-5>

[0646] [Chemical formula 32]

[0647]

[0648] Cyclohexanone (24 g) was heated to 85° C. under a nitrogen stream. While stirring the solution, a mixed solution of a monomer (14.9 g) represented by the above formula (1), a monomer (11.3 g) represented by the above formula (2), a monomer (18.9 g) represented by the above formula (3), cyclohexanone (108 g) and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (1.88 g) was added dropwise over 4 hours to obtain a reaction solution. After the addition was completed, the reaction solution was further stirred at 85° C. for 2 hours. After the obtained reaction solution was naturally cooled, it was reprecipitated with a large amount of methanol / water (mass ratio 5:5) and filtered, and the obtained solid was vacuum dried to obtain 20 g of resin A-5.

[0649] <Acid dissociation constant (pKa) of an acidic site generated by irradiation (exposure) with actinic rays or radiation>

[0650] Table 2 shows the acid dissociation constants (pKa) of the acidic sites generated by exposure in resins A-1 to A-13. In addition, with respect to resins A-1 to A-9 and resin A-11, two acidic sites derived from the anion site in the specific structural site are formed in the resin by exposure. With respect to resin A-10, an acid containing two acidic sites derived from the anion site in the specific structural site is separated from the main chain by exposure. With respect to resin A-13, one acidic site derived from the anion site in the specific structural site is formed in the resin by exposure.

[0651] When measuring the acid dissociation constant (pKa) of the acidic site generated by exposure of the resin, specifically, a compound in which the cationic site of the monomer constituting the repeating unit containing the specific structural site is substituted with a hydrogen atom is used as the object, and as described above, the value based on the database of Hammett substituent constants and known literature values ​​is calculated using the software package 1 of ACD / Labs. When pKa cannot be calculated by the above method, the value obtained by Gaussian16 based on DFT (density functional method) is used.

[0652] In the table below, "pKa1" indicates the acid dissociation constant of the first stage, and "pKa2" indicates the acid dissociation constant of the second stage. The smaller the pKa value, the higher the acidity.

[0653] In addition, pKa1 corresponds to the above-mentioned acid dissociation constant a1, and pKa2 corresponds to the above-mentioned acid dissociation constant a2.

[0654] Table 2 is shown below.

[0655] In addition, in Table 2, the structure of the resin is also shown together with the acid dissociation constant (pKa) of the acidic site generated by exposure of the resin (the "Remarks (Structure)" column in Table 2).

[0656] In the column “Is it equivalent to either specific resin X or specific resin Y” in the column “Remarks (Structure)” in Table 2, “X, Y” indicates the case where both are equivalent to either specific resin X or specific resin Y, “X” indicates the case where only specific resin X is equivalent, “Y” indicates the case where only specific resin Y is equivalent, and “-” indicates the case where neither is equivalent.

[0657] In the column "Is the monomer equivalent to compound (I)" in the column "Remarks (Structure)" in Table 2, "A" indicates that the monomer is equivalent to compound (I), and "B" indicates that the monomer is not equivalent to compound (I).

[0658] [Table 2]

[0659]

[0660] 〔Photoacid generator〕

[0661] The structures of the photoacid generators (Compounds C-1 to C-13) shown in Tables 4 and 8 are shown below.

[0662] [Chemical formula 33]

[0663]

[0664] [Chemical formula 34]

[0665]

[0666] 〔Acid diffusion control agent〕

[0667] The structures of the acid diffusion controllers (compounds D-1 to D-5) shown in Tables 4 and 8 are shown below.

[0668] [Chemical formula 35]

[0669]

[0670] 〔Hydrophobic resin and top coating resin〕

[0671] The hydrophobic resins (E-1 to E-11) shown in Tables 4 and 8 and the top coat layer resins (PT-1 to PT-3) shown in Table 5 used synthesized resins.

[0672] Table 3 shows the molar ratio, weight average molecular weight (Mw), and dispersion degree (Mw / Mn) of the repeating units in the hydrophobic resins shown in Tables 4 and 8 and the top coat layer resin shown in Table 5.

[0673] The weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) (in terms of polystyrene) of the hydrophobic resins E-1 to E-11 and the top coat resins PT-1 to PT-3 were measured by GPC (carrier: tetrahydrofuran (THF)). 13 The composition ratio (mol %) of the resin was measured by C-NMR (nuclear magnetic resonance).

[0674] [Table 3]

[0675]

[0676] The monomer structures used in the synthesis of the hydrophobic resins E-1 to E-11 shown in Tables 4 and 8 and the top coat layer resins PT-1 to PT-3 shown in Table 5 are shown below.

[0677] [Chemical formula 36]

[0678]

[0679] 〔Surfactant〕

[0680] The surfactants shown in Tables 4 and 8 are shown below.

[0681] H-1: Megaface F176 (manufactured by DIC CORPORATION, fluorine-based surfactant)

[0682] H-2: Megaface R08 (manufactured by DIC CORPORATION, fluorine and silicon surfactants)

[0683] H-3: PF656 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant)

[0684] 〔Solvent〕

[0685] The solvents shown in Table 4 and Table 8 are shown below.

[0686] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0687] F-2: Propylene glycol monomethyl ether (PGME)

[0688] F-3: Propylene glycol monoethyl ether (PGEE)

[0689] F-4: Cyclohexanone

[0690] F-5: Cyclopentanone

[0691] F-6: 2-Heptanone

[0692] F-7: Ethyl lactate

[0693] F-8: γ-Butyrolactone

[0694] F-9: Propylene carbonate

[0695] [Preparation and evaluation of actinic ray-sensitive or radiation-sensitive resin composition (1) ArF immersion exposure]

[0696] [Preparation of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition (1) ArF Immersion Exposure]

[0697] The components shown in Table 4 were mixed so that the solid content concentration became 4% by mass. Then, the obtained mixed solution was first filtered through a polyethylene filter with a pore size of 50 nm, then filtered through a nylon filter with a pore size of 10 nm, and finally filtered through a polyethylene filter with a pore size of 5 nm, thereby preparing an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as an anti-etching composition). In addition, in the anti-etching composition, the solid content represents all components except the solvent. The obtained anti-etching composition was used in the embodiments and comparative examples.

[0698] In addition, in Table 4, the content (mass %) of each component means the content relative to the total solid content.

[0699] [Table 4]

[0700]

[0701] Various components contained in the top coating composition shown in Table 5 are shown below.

[0702] <Resin>

[0703] As the resins shown in Table 5, resins PT-1 to PT-3 shown in Table 3 were used.

[0704] <Additives>

[0705] The structures of the additives shown in Table 5 are shown below.

[0706] [Chemical formula 37]

[0707]

[0708] <Surfactant>

[0709] As the surfactant shown in Table 5, the above-mentioned surfactant H-3 was used.

[0710] <Solvent>

[0711] The solvents shown in Table 5 are shown below.

[0712] FT-1: 4-Methyl-2-pentanol (MIBC)

[0713] FT-2: n-decane

[0714] FT-3: Diisoamyl ether

[0715] <Preparation of top coating composition>

[0716] The components shown in Table 5 were mixed so that the solid content concentration was 3% by mass, and then the resulting mixed solution was filtered in the order of first filtering through a polyethylene filter with a pore size of 50 nm, then filtering through a nylon filter with a pore size of 10 nm, and finally filtering through a polyethylene filter with a pore size of 5 nm, thereby preparing a top coating composition. In addition, the solid content mentioned here means all components except the solvent. The obtained top coating composition was used in the examples.

[0717] [Table 5]

[0718]

[0719] [Pattern formation (1): ArF immersion exposure, organic solvent development]

[0720] An organic anti-reflection film-forming composition ARC29SR (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflection film having a thickness of 98 nm. The resist composition shown in Table 4 was applied thereon and baked at 100°C for 60 seconds to form a resist film (photosensitive or radiation-sensitive film) having a thickness of 90 nm. In addition, for Examples 1-5, 1-6, and 1-7, a top coating film was formed on the upper layer of the resist film (the type of the top coating composition used is shown in Table 6). The thickness of the top coating film was set to 100 nm in each case.

[0721] The obtained resist film was exposed. As the exposure method, it was carried out by the method described in (A) (for LWR performance evaluation) or the method described in (B) (for EL performance evaluation) shown below.

[0722] (A) Formation of line and space patterns

[0723] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y polarization) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[0724] (B) Formation of contact hole pattern

[0725] The resist film was exposed using an ArF excimer laser liquid immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.98, inner sigma 0.89, XY deflection) through a patterning mask pattern (6% halftone) with a mask size of 45 nm and a pitch of 90 nm in the X direction and a mask size of 60 nm and a pitch of 120 nm in the Y direction. Ultrapure water was used as the liquid immersion liquid.

[0726] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds and then spin-dried to obtain a negative pattern.

[0727] <Evaluation>

[0728] (Evaluation Item 1: LWR Performance)

[0729] For a 45nm (1:1) line and space pattern analyzed with the optimal exposure when analyzing a line pattern with an average line width of 45nm, the line width was observed at any point when observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the measurement deviation was evaluated using 3σ. The smaller the value, the better the performance. In addition, LWR (nm) is preferably 3.3nm or less, more preferably 3.0nm or less, and further preferably 2.5nm or less.

[0730] (Evaluation Item 2: EL (Exposure Latitude))

[0731] The hole size in the contact hole pattern was observed by a scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the optimal exposure amount when analyzing the hole pattern with an average hole size of 45 nm in the X direction was set as the sensitivity (Eopt) (mJ / cm 2 ). Based on the obtained optimal exposure (Eopt), the exposure when the hole size becomes ±10% of the target value of 45nm (i.e., 40.5nm and 49.5nm) is then calculated. In addition, the exposure latitude (EL, %) defined by the following formula is calculated. The larger the EL value, the smaller the performance change based on the change in exposure, and the better. In addition, EL (%) is preferably 14.0% or more, and more preferably 14.5% or more.

[0732] [EL (%)] = [(exposure amount for a pore size of 40.5 nm) - (exposure amount for a pore size of 49.5 nm)] / Eopt × 100

[0733] 《Evaluation Results》

[0734] The above evaluation test results are shown in Table 6 below.

[0735] [Table 6]

[0736]

[0737] The results of Table 6 show that the pattern formed by the resist composition of the example has excellent LWR performance. Also, it is known that the resist composition of the example exhibits excellent EL performance.

[0738] Furthermore, as can be seen from the results of Table 6, when the resin contained in the resist composition is a resin containing repeating units derived from a specific compound that can generate an acid containing a polymerizable group, an acidic site derived from the anion site in the above-mentioned structural site X, and an acidic site derived from the anion site in the above-mentioned structural site Y by exposure (preferably, a resin containing repeating units derived from compound (I)), the resist composition exhibits excellent EL performance (comparison between the resist compositions using resins A-1 to A-9 and the resist composition using resin A-10).

[0739] Furthermore, from the results of Table 6, it can be seen that when the resin contained in the resist composition is a specific resin Y and the specific resin Y is a resin containing a repeating unit containing a group having a first structural part and a group having the above-mentioned second structural part (in other words, a resin containing a repeating unit containing two specific structural parts), the LWR performance of the formed pattern is better (comparison between the resist composition using resins A-1 to A-9 and the resist composition using resin A-11).

[0740] [Pattern formation (2): ArF immersion exposure, alkaline aqueous solution development]

[0741] An organic anti-reflective film-forming composition ARC29SR (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an anti-reflective film having a thickness of 98 nm. The resist composition shown in Table 4 was applied thereon and baked at 100°C for 60 seconds to form a resist film having a thickness of 90 nm. In addition, for Examples 2-3 and 2-5 to 2-7, a top coating film was formed on the upper layer of the resist film (the type of top coating composition used is shown in Table 7). The thickness of the top coating film was set to 100 nm in each case.

[0742] The obtained resist film was exposed. As the exposure method, it was carried out by the method described in (A) (for LWR performance evaluation) or the method described in (B) (for EL performance evaluation) shown below.

[0743] (A) Formation of line and space patterns

[0744] The resist film was exposed using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.890, Y deflection) through a 6% halftone mask of a 1:1 line and space pattern with a line width of 45 nm. Ultrapure water was used as the immersion liquid.

[0745] (B) Formation of contact hole pattern

[0746] The resist film was exposed using an ArF excimer laser liquid immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.98, inner sigma 0.89, XY deflection) through a patterning mask pattern (6% halftone) with a mask size of 45 nm and a pitch of 90 nm in the X direction and a mask size of 60 nm and a pitch of 120 nm in the Y direction. Ultrapure water was used as the liquid immersion liquid.

[0747] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds and spin-dried to obtain a positive pattern.

[0748] The obtained positive pattern was subjected to performance evaluation (line width roughness (LWR, nm), exposure latitude (EL, %)) using the negative pattern obtained in the above [Pattern formation (1): ArF liquid immersion exposure, organic solvent development].

[0749] 《Evaluation Results》

[0750] The above evaluation test results are shown in Table 7 below.

[0751] [Table 7]

[0752]

[0753] The results of Table 7 show that the pattern formed by the resist composition of the example has excellent LWR performance. Also, it is known that the resist composition of the example exhibits excellent EL performance.

[0754] Furthermore, as can be seen from the results of Table 7, when the resin contained in the resist composition is a resin containing repeating units derived from a specific compound that can generate an acid containing a polymerizable group, an acidic site derived from the anion site in the above-mentioned structural site X, and an acidic site derived from the anion site in the above-mentioned structural site Y by exposure (preferably a resin containing repeating units derived from compound (I)), the resist composition exhibits excellent EL performance (comparison between the resist compositions using resins A-1 to A-9 and the resist composition using resin A-10).

[0755] Furthermore, from the results of Table 7, it can be seen that when the resin contained in the resist composition is a specific resin Y and the specific resin Y is a resin containing a repeating unit containing a group having a first structural part and a group having the above-mentioned second structural part (in other words, a resin containing a repeating unit containing two specific structural parts), the LWR performance of the formed pattern is better (comparison between the resist composition using resins A-1 to A-9 and the resist composition using resin A-11).

[0756] [Preparation and evaluation of actinic ray-sensitive or radiation-sensitive resin compositions (2) EUV exposure]

[0757] [Preparation of photosensitive or radiation-sensitive resin composition (2) EUV exposure]

[0758] The components shown in Table 8 were mixed so that the solid content concentration was 2% by mass. Then, the resulting mixed solution was first filtered through a polyethylene filter with a pore size of 50 nm, then filtered through a nylon filter with a pore size of 10 nm, and finally filtered through a polyethylene filter with a pore size of 5 nm, thereby preparing an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as an anti-etching composition). In addition, in the anti-etching composition, the solid content refers to all components except the solvent.

[0759] The obtained resist composition was used in Examples and Comparative Examples.

[0760] [Table 8]

[0761]

[0762] [Pattern formation (3): EUV exposure, organic solvent development]

[0763] The lower film-forming composition AL412 (manufactured by Brewer Science) was applied on the silicon wafer and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The resist composition shown in Table 8 was applied thereon and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[0764] The silicon wafer with the obtained resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a mask, a mask with line size = 20 nm and line: space = 1:1 was used.

[0765] The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

[0766] <Evaluation>

[0767] (Evaluation Item 1: LWR Performance)

[0768] For a 20nm (1:1) line and space pattern analyzed with the optimal exposure when analyzing a line pattern with an average line width of 20nm, the line width was observed at any point when observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and its measurement deviation was evaluated using 3σ. The smaller the value, the better the performance. In addition, LWR (nm) is preferably 4.2nm or less, more preferably 4.0nm or less, further preferably 3.8nm or less, and particularly preferably 3.7nm or less.

[0769] (Evaluation Item 2: EL (Exposure Latitude))

[0770] The line width in line and space was observed by a scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the optimal exposure amount when analyzing a pattern with an average of 20 nm was defined as sensitivity (Eopt) (mJ / cm 2 ). Based on the obtained optimal exposure (Eopt), the exposure when the line width becomes ±10% of the target value of 20nm (i.e., 18.0nm and 22.0nm) is then calculated. In addition, the exposure latitude (EL, %) defined by the following formula is calculated. The larger the EL value, the smaller the performance change based on the change in exposure, and the better. In addition, EL (%) is preferably 20.0% or more, and more preferably 21.0% or more.

[0771] [EL (%)] = [(exposure amount for a pore size of 18.0 nm) - (exposure amount for a pore size of 22.0 nm)] / Eopt × 100

[0772] 《Evaluation Results》

[0773] The above evaluation test results are shown in Table 9 below.

[0774] [Table 9]

[0775]

[0776] The results of Table 9 show that the pattern formed by the resist composition of the example has excellent LWR performance. Also, it is known that the resist composition of the example exhibits excellent EL performance.

[0777] Furthermore, as can be seen from the results of Table 9, when the resin contained in the resist composition is a resin containing repeating units derived from a specific compound that can generate an acid containing a polymerizable group, an acidic site derived from the anion site in the above-mentioned structural site X, and an acidic site derived from the anion site in the above-mentioned structural site Y by exposure (preferably a resin containing repeating units derived from compound (I)), the resist composition exhibits excellent EL performance (comparison between the resist compositions using resins A-1 to A-9 and the resist composition using resin A-10).

[0778] Furthermore, from the results of Table 9, it can be seen that when the resin contained in the resist composition is a specific resin Y and the specific resin Y is a resin containing a repeating unit including a group having a first structural part and a group having the above-mentioned second structural part (in other words, a resin containing a repeating unit including two specific structural parts), the LWR performance of the pattern formed is better (comparison between the resist composition using resins A-1 to A-9 and the resist composition using resin A-11).

[0779] [Pattern formation (4): EUV exposure, alkaline aqueous solution development]

[0780] The lower film-forming composition AL412 (manufactured by Brewer Science) was applied on the silicon wafer and baked at 205°C for 60 seconds to form a base film with a thickness of 20 nm. The resist composition shown in Table 8 was applied thereon and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[0781] The silicon wafer with the obtained resist film was pattern irradiated using an EUV exposure device (manufactured by Exitech Corporation, Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). In addition, as a mask, a mask with line size = 20 nm and line: space = 1:1 was used.

[0782] The exposed resist film was baked at 90° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds and spin-dried to obtain a positive pattern.

[0783] The obtained positive pattern was subjected to performance evaluation (line width roughness (LWR, nm), exposure latitude (EL, %)) using the negative pattern obtained in the above [Pattern formation (3): EUV exposure, organic solvent development].

[0784] 《Evaluation Results》

[0785] The above evaluation test results are shown in Table 10 below.

[0786] [Table 10]

[0787]

[0788] The results in Table 10 show that the pattern formed by the resist composition of the example has excellent LWR performance. Also, it is known that the resist composition of the example exhibits excellent EL performance.

[0789] Furthermore, as can be seen from the results in Table 10, when the resin contained in the resist composition is a resin containing repeating units derived from a specific compound that can generate an acid containing a polymerizable group, an acidic site derived from the anion site in the above-mentioned structural site X, and an acidic site derived from the anion site in the above-mentioned structural site Y by exposure (preferably a resin containing repeating units derived from compound (I)), the resist composition exhibits excellent EL performance (comparison between the resist compositions using resins A-1 to A-9 and the resist composition using resin A-10).

[0790] Furthermore, from the results in Table 10, it can be seen that when the resin contained in the resist composition is a specific resin Y and the specific resin Y is a resin containing a repeating unit including a group having a first structural part and a group having the above-mentioned second structural part (in other words, a resin containing a repeating unit including two specific structural parts), the LWR performance of the formed pattern is better (comparison between the resist composition using resins A-1 to A-9 and the resist composition using resin A-11).

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition, comprising a resin X, wherein the resin X comprises a repeating unit derived from the following compound: A compound comprising two or more structural parts consisting of an anion part and a cation part and a polymerizable group, and generating an acid containing an acidic part derived from the anion part of the two or more structural parts by irradiation with actinic rays or radiation, In the compound, two or more of the anion sites have structures different from each other.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein The compound is the following compound (I), Compound (I): having at least one of each of the following structural part X and the following structural part Y, and having a polymerizable group, wherein the compound generates an acid containing the polymerizable group, the following first acidic part derived from the following structural part X, and the following second acidic part derived from the following structural part Y by irradiation with actinic rays or radiation, Structural site X: Anionic site A1 - and cationic site M1 + and by irradiation with actinic rays or radiation, a structural part of the first acidic part represented by HA1 is formed. Structural site Y: Anionic site A2 - and cationic site M2 + and, by irradiation with actinic rays or radiation, a second acidic site represented by HA2 having a structure different from that of the first acidic site formed by the structural site X is formed. Wherein, compound (I) satisfies the following condition I, Condition I: In the compound (I), the cationic site M1 in the structural site X is + and the cationic site M2 in the structural site Y + Replaced by H + The compound PI has an acid dissociation constant a1, which is derived from the cationic site M1 in the structural site X. + Replaced by H + and an acid dissociation constant a2 derived from the cationic site M2 in the structural site Y. + Replaced by H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein The resin X further contains a repeating unit having an acid-decomposable group.

4. An actinic ray-sensitive or radiation-sensitive resin composition comprising the following resin Y, Resin Y: It contains: Acid decomposable groups; a group having a first structural part consisting of a first anion part and a first cation part; and a group having a second structural part consisting of a second anion part and a second cation part, The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation, The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation, The second acidic site has a structure different from that of the first acidic site, and has an acid dissociation constant greater than that of the first acidic site.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein The resin Y contains: a repeating unit comprising the acid-decomposable group; and A repeating unit comprising a group having the first structural part and a group having the second structural part. 6 . A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 .

7. A pattern forming method comprising the following steps: A step of forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5; a step of exposing the resist film to light; and A step of developing the exposed resist film using a developer.

8. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 7.

9. A compound comprising two or more structural parts consisting of an anionic part and a cationic part and a polymerizable group, An acid containing an acidic site derived from the anion site in the two or more structural sites is generated by irradiation with actinic rays or radiation, Two or more of the anion sites have structures different from each other.

10. The compound according to claim 9, which is the following compound (I), Compound (I): having at least one of each of the following structural part X and the following structural part Y, and having a polymerizable group, wherein the compound generates an acid containing the polymerizable group, the following first acidic part derived from the following structural part X, and the following second acidic part derived from the following structural part Y by irradiation with actinic rays or radiation, Structural site X: Anionic site A1 - and cationic site M1 + and by irradiation with actinic rays or radiation, a structural part of the first acidic part represented by HA1 is formed. Structural site Y: Anionic site A2 - and cationic site M2 + and, by irradiation with actinic rays or radiation, a second acidic site represented by HA2 having a structure different from that of the first acidic site formed by the structural site X is formed. in, Compound (I) satisfies the following condition I, Condition I: In the compound (I), the cationic site M1 in the structural site X is + and the cationic site M2 in the structural site Y + Replaced by H + The compound PI has an acid dissociation constant a1, which is derived from the cationic site M1 in the structural site X. + Replaced by H + and an acid dissociation constant a2 derived from the cationic site M2 in the structural site Y. + Replaced by H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1. 11 . A resin comprising a repeating unit derived from the compound according to claim 9 or 10. 12 . The resin according to claim 11 , further comprising a repeating unit having an acid-decomposable group.

13. A resin comprising: Acid decomposable groups; a group having a first structural part consisting of a first anion part and a first cation part; and a group having a second structural part consisting of a second anion part and a second cation part, The first structural site forms a first acidic site derived from the first anionic site by irradiation with actinic rays or radiation, The second structural site forms a second acidic site derived from the second anionic site by irradiation with actinic rays or radiation, The second acidic site has a structure different from that of the first acidic site, and has an acid dissociation constant greater than that of the first acidic site.

14. The resin according to claim 13, comprising: a repeating unit comprising the acid-decomposable group; and A repeating unit comprising a group having the first structural part and a group having the second structural part.

Images