Method for producing resist composition and method for testing resist composition

Abstract

To provide a method for producing a resist composition which can produce a resist composition having fixed sensitivity and line width roughness with high accuracy, and a method for assaying a resist composition which can assay whether the resist composition is a resist composition having fixed sensitivity and line width roughness.SOLUTION: There are provided a method for producing a resist composition which includes a step (1) of acquiring reference data using a reference resist composition A containing an optical acid generator and a resin, a step (2) of acquiring measurement data using a resist composition B for measurement containing a component of the same kind as a component contained in the reference resist composition A, a step (3) of comparing reference data with the measurement data, and determining whether or not the resist composition is within an allowable range, and a step (4) of preparing a resist composition C having a different percentage content of the resin from that of the resist composition B for measurement, when determining that it is not within the allowable range in the step (3); and a method for assaying a resist composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a resist composition and a method for testing a resist composition, and more particularly to a method for producing a resist composition and a method for testing a resist composition that can be suitably used in ultra-microlithography processes applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. In recent years, the increasing integration density of integrated circuits has led to a demand for ultrafine pattern formation in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as a light source have been developed. Furthermore, as a technology for further improving resolution, the so-called immersion method, in which a high-refractive-index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] Furthermore, methods for evaluating resins used in resist compositions have also been investigated. For example, Patent Document 1 describes a method for evaluating a radiation-sensitive resin, in which dynamic light scattering of a solution of the radiation-sensitive resin in a resist solvent is measured, and the development characteristics of the radiation-sensitive resin are evaluated based on a coefficient that represents a change in the diffusion coefficient of the radiation-sensitive resin in the solution that accompanies a change in the concentration of the solution. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-91407 Summary of the Invention [Problem to be solved by the invention]

[0006] Typically, a resist composition contains a resin and a photoacid generator, but due to quality variations between lots and the effects of impurities, it can be difficult to prepare a resist composition with consistent sensitivity (within an acceptable range of deviation from the target value) even when the same types and amounts of components are used. Furthermore, there is no description whatsoever of a method for preparing a resist composition with a consistent sensitivity, which is affected by quality variations between lots and the influence of impurities.

[0007] The present inventors first investigated a method for adjusting the sensitivity of a resist composition by adjusting the content ratio of the photoacid generator and the acid diffusion controller contained in the resist composition. However, even if the sensitivity of the resist composition can be controlled to a certain degree using the above method, other properties (e.g., roughness) may deviate. In particular, resist compositions for EUV exposure used in forming ultrafine patterns (e.g., line widths of 30 nm or less) require strict quality control of not only sensitivity but also other properties, such as roughness. It is also desirable to further improve the precision with which resist compositions with constant sensitivity and line width roughness (LWR) are manufactured. An object of the present invention is to provide a method for producing a resist composition that can produce a resist composition with consistent sensitivity and line width roughness (LWR) with high precision, and a method for testing a resist composition that can test whether a resist composition has consistent sensitivity and line width roughness (LWR). [Means for solving the problem]

[0008] The present inventors have found that the above problems can be solved by the following configuration. <1> a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and an acid-decomposable resin, exposing the resist film A to light, and developing the resist film A to form a resist pattern A, thereby obtaining reference data; a step (2) of forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A but in the same amounts as those in a different lot, exposing the resist film B to light, developing the resist film B, and obtaining measurement data; a step (3) of comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a different content of the acid-decomposable resin from that of the resist composition B for measurement, if the result of the step (3) is determined to be outside the allowable range; Including, At least one of the following (a) and (b) is carried out, and at least one of the following (i), (ii) and (iii) is carried out: A method for producing a resist composition. (a) The above-mentioned standard data and the above-mentioned measurement data are sensitivity data, and the value obtained by subtracting the above-mentioned standard data from the above-mentioned measurement data is within ±0.5% of the above-mentioned standard data, which is within the above-mentioned tolerance range. (i) The above-mentioned standard data and the above-mentioned measurement data are line width roughness data, and the value obtained by subtracting the above-mentioned standard data from the above-mentioned measurement data is within ±2.0% of the above-mentioned standard data, which is within the above-mentioned tolerance range. (i) In the above step (4), a step of measuring the EUV absorption efficiency of the resist film is carried out, and the EUV absorption efficiency S1 of the resist film A is A and the EUV absorption efficiency S1 of the resist film C formed using the resist composition C. C The difference between the above S1 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±0.3%. (ii) In the above step (4), a step of measuring the glass transition temperature of the resist film is carried out, and the glass transition temperature S2 of the resist film A is measured. A and the glass transition temperature S2 of the resist film C formed using the resist composition C. C The difference between the above S2 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±0.5%. (iii) In the step (4), a step of measuring the dissolution rate of the resist film in the developer is carried out, and the dissolution rate S3 of the resist film A in the developer is A and the dissolution rate S3 of the resist film C formed using the resist composition C in the developer. C The difference between the above S3 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±2.0%. <2> The photoacid generator contains at least one of the following compounds (I) and (II): <1> 10. A method for producing the resist composition according to claim 9. Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which generates an acid containing a first acidic moiety derived from the structural moiety Z1 and a second acidic moiety derived from the structural moiety Z2 when irradiated with actinic rays or radiation: Structural site Z1: Anion site A 1 - and cationic moiety M 1 + and HA by irradiation with actinic rays or radiation. 1 The structural moiety forming the first acidic site is represented by Structural site Z2: Anion site A 2 - and cationic moiety M 2 + and HA by irradiation with actinic rays or radiation. 2 The structural moiety forming the second acidic site is represented by However, compound (I) satisfies the following condition I. Condition I: In the compound (I), the cation moiety M in the structural moiety Z1 1 + and the cationic moiety M in the structural moiety Z2 2 + H + The compound PI in which the cationic moiety M in the structural moiety Z1 is replaced by 1 + H + HA is replaced by 1 and the cationic moiety M in the structural moiety Z2. 2 + H + HA is replaced by 2 and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II): A compound having two or more of the above structural moieties Z1 and one or more of the following structural moieties Z3, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety Z1 and the structural moiety Z3 when irradiated with actinic rays or radiation. Structural site Z3: a non-ionic site capable of neutralizing acids <3> the reference resist composition A further contains an acid diffusion controller Qb different from the compounds (I) and (II); <2> 10. A method for producing the resist composition according to claim 9. <4> The number of moles of photodecomposable cations contained in the reference resist composition A is P A , Q represented by the following formula (a) for the reference resist composition A is Q A The number of moles of photodecomposable cations contained in the resist composition C is P C For the resist composition C, Q represented by the following formula (a) is C Then, Q A / P A From Q C / P C The value obtained by subtracting A / P A The value is within ±0.3% of the <2> or <3> 10. A method for producing the resist composition according to claim 9. Q = (number of Z2 in one molecule of compound (I)) × (number of moles of compound (I)) + (number of Z3 in one molecule of compound (II)) × (number of moles of compound (II)) + (number of moles of acid diffusion controller Qb) (a) However, the acid diffusion controller Qb is a compound different from the above compounds (I) and (II). <5> The solid content concentration of the above reference resist composition A is E A The solid content concentration of the resist composition C is E C When the above E A and the above EC The difference between the above E A Within ±2.0% of <1> ~ <4> 10. A method for producing a resist composition according to any one of the above items. <6> The light source used for the exposure is EUV. <1> ~ <5> 10. A method for producing a resist composition according to any one of the above items. <7> a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and an acid-decomposable resin, exposing the resist film A to light, and developing the resist film A to form a resist pattern A, thereby obtaining reference data; a step (2) of forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A but in the same amounts as those in a different lot, exposing the resist film B to light, developing the resist film B, and obtaining measurement data; a step (3) of comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a different content of the acid-decomposable resin from that of the resist composition B for measurement, if the result of the step (3) is determined to be outside the allowable range; Including, A method for testing a resist composition, comprising: performing at least one of the following (a) and (b) and at least one of the following (i), (ii) and (iii): (a) The above-mentioned standard data and the above-mentioned measurement data are sensitivity data, and the value obtained by subtracting the above-mentioned standard data from the above-mentioned measurement data is within ±0.5% of the above-mentioned standard data, which is within the above-mentioned tolerance range. (i) The above-mentioned standard data and the above-mentioned measurement data are line width roughness data, and the value obtained by subtracting the above-mentioned standard data from the above-mentioned measurement data is within ±2.0% of the above-mentioned standard data, which is within the above-mentioned tolerance range. (i) In the above step (4), a step of measuring the EUV absorption efficiency of the resist film is carried out, and the EUV absorption efficiency S1 of the resist film A is A and the EUV absorption efficiency S1 of the resist film C formed using the resist composition C. C The difference between the above S1 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±0.3%. (ii) In the above step (4), a step of measuring the glass transition temperature of the resist film is carried out, and the glass transition temperature S2 of the resist film A is measured. A and the glass transition temperature S2 of the resist film C formed using the resist composition C. C The difference between the above S2 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±0.5%. (iii) In the step (4), a step of measuring the dissolution rate of the resist film in the developer is carried out, and the dissolution rate S3 of the resist film A in the developer is A and the dissolution rate S3 of the resist film C formed using the resist composition C in the developer. C The difference between the above S3 A The resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference is within ±2.0%. The present invention relates to the above <1> ~ <7> However, other matters are incorporated herein by reference.

[0009] [1] a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and a resin, exposing the resist film A to light, developing the resist film A to form a resist pattern A, and acquiring reference data; a step (2) of forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A, exposing the resist film B, and developing the resist film B to form a resist pattern B, thereby obtaining measurement data; a step (3) of comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a resin content different from that of the resist composition B for measurement if it is determined in the step (3) that the resin content is not within the allowable range; A method for producing a resist composition, comprising: [2] The method for producing a resist composition according to [1], wherein the photoacid generator comprises at least one of the following compounds (I) and (II): Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which generates an acid containing a first acidic moiety derived from the structural moiety Z1 and a second acidic moiety derived from the structural moiety Z2 when irradiated with actinic rays or radiation: Structural site Z1: Anion site A1 - and cationic moiety M1 + and a structural portion that forms a first acidic site represented by HA1 upon irradiation with actinic rays or radiation. Structural site Z2: Anionic site A2 - and cationic moiety M2 + and a structural portion that forms a second acidic site represented by HA2 upon irradiation with actinic rays or radiation. However, compound (I) satisfies the following condition I. Condition I: In the compound (I), the cation moiety M1 in the structural moiety Z1 + and the cationic moiety M2 in the structural moiety Z2 + H + The compound PI in which the cationic moiety M1 in the structural moiety Z1 is replaced by + H + and the cationic moiety M2 in the structural moiety Z2. + H + and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II): A compound having two or more of the above structural moieties Z1 and one or more of the following structural moieties Z3, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety Z1 and the structural moiety Z3 when irradiated with actinic rays or radiation. Structural site Z3: a non-ionic site capable of neutralizing acids [3] The method for producing a resist composition according to [2], wherein the reference resist composition A further contains an acid diffusion controller Qb that is different from the compounds (I) and (II). [4] The number of moles of photodecomposable cations contained in the reference resist composition A is P A , Q represented by the following formula (a) for the reference resist composition A is Q A The number of moles of photodecomposable cations contained in the resist composition C is P C For the resist composition C, Q represented by the following formula (a) is C Then, Q A / P A From Q C / P C The value obtained by subtracting A / P A The method for producing a resist composition according to [2] or [3], wherein the value is within ±0.3% of the value of Q = (number of Z2 in one molecule of compound (I)) × (number of moles of compound (I)) + (number of Z3 in one molecule of compound (II)) × (number of moles of compound (II)) + (number of moles of acid diffusion controller Qb) (a) However, the acid diffusion controller Qb is a compound different from the above compounds (I) and (II). [5] The method for producing a resist composition according to any one of [1] to [4], wherein the resin is an acid-decomposable resin. [6] The method for producing a resist composition according to any one of [1] to [5], wherein the reference data and the measurement data are sensitivity data, and the tolerance is defined as being within ±0.5% of the reference data when the value obtained by subtracting the reference data from the measurement data is within ±0.5% of the reference data. [7] The method for producing a resist composition according to any one of [1] to [6], wherein the reference data and the measured data are data on line width roughness, and the tolerance is defined as being within ±2.0% of the reference data when the value obtained by subtracting the reference data from the measured data is within ±2.0% of the reference data. [8] In the step (4), the EUV absorption efficiency S1 of the resist film A A and the EUV absorption efficiency S1 of the resist film C formed using the resist composition C. C The method for producing a resist composition according to any one of [1] to [7], wherein the resist composition C is prepared by changing the content of the resin in the resist composition B for measurement so that the difference between the [9] S1 above A and S1 above C The difference between the above S1 A The method for producing a resist composition according to [8], wherein the predetermined range is within ±0.3% of the above.

[10] In the above step (4), the glass transition temperature S2 of the resist film A A and the glass transition temperature S2 of the resist film C formed using the resist composition C. C The method for producing a resist composition according to any one of [1] to [7], wherein the resist composition C is prepared by changing the content of the resin in the resist composition B for measurement so that the difference between the

[11] S2 above A and S2 above C The difference between the above S2 A The method for producing a resist composition according to

[10] , wherein the predetermined range is within ±0.5% of the above.

[12] In the step (4), the dissolution rate S3 of the resist film A in the developer A and the dissolution rate S3 of the resist film C formed using the resist composition C in the developer. CThe method for producing a resist composition according to any one of [1] to [7], wherein the resist composition C is prepared by changing the content of the resin in the resist composition B for measurement so that the difference between the

[13] S3 above A and S3 above C The difference between the above S3 A The method for producing a resist composition according to

[12] , wherein the predetermined range is within ±2.0% of the above.

[14] The solid content concentration of the above reference resist composition A is E A The solid content concentration of the resist composition C is E C When the above E A and the above E C The difference between the above E A The method for producing a resist composition according to any one of [1] to

[13] , wherein the difference is within ±2.0%.

[15] The method for producing a resist composition according to any one of [1] to

[14] , wherein the light source used for the exposure is EUV.

[16] a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and a resin, exposing the resist film A to light, developing the resist film A to form a resist pattern A, and acquiring reference data; a step (2) of forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A, exposing the resist film B, and developing the resist film B to form a resist pattern B, thereby obtaining measurement data; a step (3) of comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a resin content different from that of the resist composition B for measurement if it is determined in the step (3) that the resin content is not within the allowable range; A method for testing a resist composition, comprising: [Effects of the Invention]

[0010] The present invention provides a method for producing a resist composition that can produce a resist composition with consistent sensitivity and line width roughness (LWR) with high precision, and a method for testing a resist composition that can test whether a resist composition has consistent sensitivity and line width roughness (LWR). DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" means actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV, and the like, but also drawing using particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0013] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0014] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) 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: refractive index detector).

[0015] In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom, which can be selected from the following substituents T.

[0016] (substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; cycloalkyloxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group and butoxycarbonyl group; cycloalkyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0017] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. The compound may be "X-CO-OZ" or "XO-CO-Z".

[0018] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0019] The pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + One method is to calculate the dissociation free energy. + The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian 16.

[0020] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett's substituent constants and known literature values, as described above. However, if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0021] In this specification, the "solids" of a resist composition refers to the components of the resist composition that form a resist film, and does not include solvents. Furthermore, any component that forms a resist film is considered to be a solid, even if it is in a liquid state.

[0022] <Method of manufacturing resist composition> The method for producing the resist composition of the present invention (also referred to as the "production method of the present invention") is as follows: a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and a resin, exposing the resist film A, and developing the resist film A to form a resist pattern A, thereby obtaining reference data; a step (2) of forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A, exposing the resist film B, and developing the resist film B to form a resist pattern B, thereby obtaining measurement data; a step (3) of comparing the reference data with the measured data to determine whether the measured data is within an acceptable range; and If it is determined in step (3) that the resin content is not within the allowable range, a step (4) of preparing a resist composition C having a resin content different from that of the resist composition B for measurement. A method for producing a resist composition comprising the steps of:

[0023] The reason why the production method of the present invention enables a resist composition with consistent sensitivity and LWR to be produced with high precision is not necessarily clear, but the inventors of the present invention speculate as follows. In a method of adjusting the content ratio of the photoacid generator to the acid diffusion controller in a resist composition to correct a deviation in sensitivity of a resist composition, it is not possible to necessarily correct the effects on the physical properties of the resist film due to quality variations between lots, the effects of impurities, etc., and this can result in deviations in performance other than sensitivity (e.g., LWR). In contrast, the present invention adjusts the resin content in the resist composition (the amount of resin relative to the total solid content in the resist composition), which makes it possible to correct the effects on the physical properties of the resist film due to quality variations between lots, the effects of impurities, etc., and is thought to suppress deviations in performance other than sensitivity (LWR).

[0024] The production method of the present invention includes at least the above steps (1) to (4). The production method of the present invention may include other steps in addition to steps (1) to (4).

[0025] [Step (1) and Step (2)] Step (1) is a step of forming a resist film A using a reference resist composition A (also referred to as "composition A") containing a photoacid generator and a resin, exposing the resist film A, developing it, forming a resist pattern A, and obtaining reference data. Composition A used in step (1) is a reference resist composition. The components contained in Composition A will be described in detail below. The reference data obtained in step (1) is preferably data on at least one of sensitivity and LWR, more preferably data on sensitivity and LWR. The light source used for exposure is not limited, but examples include KrF, ArF, EUV, and electron beams, with EUV or electron beams being preferred, and EUV being more preferred. The resist pattern A may be any pattern, but examples include a line-and-space pattern with a line:space ratio of 1:1, and a line-and-space pattern with a line width of 30 nm or less is preferred. The details of the exposure and development processes will be described later.

[0026] Step (2) is a step of forming a resist film B using a measurement resist composition B (also referred to as "composition B") containing the same types of components as those contained in composition A, exposing the resist film B, developing it, forming a resist pattern B, and acquiring measurement data. Composition B used in step (2) is a resist composition prepared separately from composition A. Composition B used in step (2) contains the same types of components as those contained in composition A, and is typically prepared using the same types of components as those contained in composition A in the same amounts. The components contained in composition B are the same as those contained in composition A, and will be described in detail below. The measurement data obtained in step (2) is preferably the same type of data as the reference data, and is preferably data on sensitivity and LWR. The light source used for exposure is not limited, but is preferably the same as that used in step (1), and examples include KrF, ArF, EUV, and electron beams. EUV or electron beams are preferred, and EUV is more preferred. Resist pattern B may be any pattern, but is preferably the same pattern as resist pattern A, and examples include a line-and-space pattern with a line:space ratio of 1:1, and a line-and-space pattern with a line width of 30 nm or less is preferred. The exposure and development treatments are the same as those in step (1), and will be described in detail later.

[0027] The order in which steps (1) and (2) are performed is not limited, and steps (1) and (2) may be performed simultaneously.

[0028] [Process (3)] Step (3) is a step of comparing the reference data with the measured data to determine whether or not the measured data is within an allowable range. The reference data and measurement data are sensitivity data, and the value obtained by subtracting the reference data from the measurement data is preferably within ±0.5% of the reference data, more preferably within ±0.4%, and even more preferably within ±0.3%. In other words, the sensitivity reference data is K1 A The measured sensitivity data is K1 B When this is the case, -0.5≦100×(K1 B -K1 A ) / K1 A It is preferable that −0.5>100×(K1 B -K1 A ) / K1 A In the case of , or 100 × (K1 B -K1 A ) / K1 A If the sensitivity is greater than 0.5, it is preferable to determine that the sensitivity is not within the acceptable range. The unit of sensitivity is typically "mJ / cm" when the light source used for exposure is KrF, ArF, EUV, etc. 2 " and for electron beams, it is typically "μC / cm 2 "

[0029] Furthermore, when the reference data and the measurement data are LWR data, it is preferable that the value obtained by subtracting the reference data from the measurement data is within ±2.0% of the reference data, and it is more preferable that it is within ±1.5%, and even more preferable that it is within ±1.0%. In other words, the LWR reference data is K2 A The measured data of LWR is K2 B When this is the case, -2.0≦100×(K2 B -K2 A ) / K2 A It is preferable that −2.0>100×(K2 B -K2 A ) / K2 A In the case of , or 100 × (K2 B -K2 A ) / K2 A If the LWR is greater than 2.0, it is preferably determined to be outside the acceptable range. The unit of LWR is typically "nm."

[0030] [Process (4)] Step (4) is a step of preparing a resist composition C (also referred to as "composition C") having a resin content different from that of measurement resist composition B when it is determined in step (3) that the resin content is not within the acceptable range. Resist composition C is a resist composition containing the same types of components as the components contained in reference resist composition A. A resist film C is formed using resist composition C, and the resist film C is exposed and developed to form a resist pattern C. The data C obtained by comparing it with the reference data preferably falls within the allowable range of step (3). That is, in step (4), when it is determined in step (3) that the resin content is not within the allowable range, the content of the resin in composition B is referred to, and the content of the resin is changed (increased or decreased) to prepare resist composition C. When the content of the resin is changed (increased or decreased), the content of the resin in composition A is changed to L A The resin content of composition C is L C In this case, -5.0≦100×(L C -L A ) / L A <0.0, or 0.0<100×(L C -L A ) / L A It is preferable to change the range of -3.0≦100×(L C -L A ) / L A <0.0, or 0.0<100×(L C -L A ) / L A It is more preferable to change it in the range of -1.0≦100×(L C -L A ) / L A <0.0, or 0.0<100×(L C -L A ) / L A It is more preferable to change it in the range of ≦1.0.

[0031] Composition C prepared in step (4) is a resist composition prepared separately from compositions A and B. Composition C contains the same types of ingredients as those contained in Compositions A and B. The components contained in composition C are the same as those contained in compositions A and B, and will be described in detail below. The data C is preferably the same type of data as the reference data and the measurement data, and is preferably data on sensitivity and LWR. The light source used for exposure when acquiring the data C is not limited, but is preferably the same as that used in step (1), and examples thereof include KrF, ArF, EUV, and electron beams. EUV or electron beams are preferred, and EUV is more preferred. The resist pattern C may be any pattern, but is preferably the same pattern as the resist pattern A, and examples thereof include a line-and-space pattern with a line:space ratio of 1:1, and a line-and-space pattern with a line width of 30 nm or less is preferred. The exposure and development treatments are the same as those in step (1), and will be described in detail later.

[0032] The solid concentration of composition A is E A , the solid content concentration of composition C is E C When E A and E C The difference is E A It is preferably within ±2.0%, more preferably within ±1.0%, and even more preferably within ±0.5%. That is, -2.0≦100×(E C -E A ) / E A It is preferred that it is ≦2.0.

[0033] In step (4), the resin whose content is changed is preferably an acid-decomposable resin, the details of which will be described later.

[0034] When changing the resin content in step (4), it is preferable to use at least one of the following as a guideline: the EUV absorption efficiency of the resist film, the glass transition temperature (Tg) of the resist film, and the dissolution rate of the resist film in a developer. These are physical properties of the resist film and are related to sensitivity and LWR, so using these as a guideline allows step (4) to be completed more quickly.

[0035] In step (4), the EUV absorption efficiency S1 of the resist film A formed using the composition A is A and the EUV absorption efficiency S1 of the resist film C formed using the composition C. C It is preferable to prepare composition C by changing the resin content in composition B so that the difference between the EUV absorption efficiencies falls within a predetermined range. If the difference in the EUV absorption efficiencies of the resist films is not within the predetermined range even after changing the resin content, attempts can be made to repeatedly change the resin content until the difference falls within the predetermined range. S1 A and S1 C The difference between S1 A It is preferable that the predetermined range be within ±0.3%, more preferably within ±0.2%, and even more preferably within ±0.1%. That is, -0.3≦100×(S1 C -S1 A ) / S1 A It is preferred that it is ≦0.3.

[0036] The EUV absorption efficiency can be calculated from the A value obtained by the following formula (1): When the A value is high, the EUV absorption efficiency of the resist film formed from the resist composition increases. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)

[0037] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solid content to all atoms in all solid content in the resist composition, [C] represents the molar ratio of carbon atoms derived from all solid content to all atoms in all solid content in the resist composition, [N] represents the molar ratio of nitrogen atoms derived from all solid content to all atoms in all solid content in the resist composition, [O] represents the molar ratio of oxygen atoms derived from all solid content to all atoms in all solid content in the resist composition, [F] represents the molar ratio of fluorine atoms derived from all solid content to all atoms in all solid content in the resist composition, [S] represents the molar ratio of sulfur atoms derived from all solid content to all atoms in all solid content in the resist composition, and [I] represents the molar ratio of iodine atoms derived from all solid content to all atoms in all solid content in the resist composition.

[0038] The A value can be calculated by calculating the atomic ratio of the components contained in the resist composition when the structure and content of all solid components in the resist composition are known. Even when the components are unknown, the atomic ratio of the components can be calculated by analytical techniques such as elemental analysis of the resist film obtained by evaporating the solvent component of the resist composition.

[0039] In step (4), the glass transition temperature S2 of the resist film A A and the glass transition temperature S2 of resist film C C It is preferable to prepare composition C by changing the resin content in composition B so that the difference between the Tg values ​​falls within a predetermined range. If the difference in Tg between the resist films is not within the predetermined range even after changing the resin content, repeated attempts to change the resin content can be made until the difference falls within the predetermined range. S2 A and S2 C The difference between S2 A It is preferable that the predetermined range be within ±0.5%, more preferably within ±0.4%, and even more preferably within ±0.3%. That is, -0.5≦100×(S2 C -S2 A ) / S2 A It is preferred that it is ≦0.5. The unit of the glass transition temperature is typically "°C".

[0040] The Tg of the resist film can be calculated as the product of the "Tg of the resin" and the "content (mass %) of the resin in the solid content of the resist composition." The "Tg of the resin" can be calculated using the following method. The Tg of each homopolymer consisting of only each repeating unit contained in the resin is calculated using the Bicerano method. Hereinafter, the calculated Tg is referred to as the "Tg of the repeating unit." Next, the mass percentage (%) of each repeating unit relative to all repeating units in the resin is calculated. Next, the Tg for each mass percentage is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​is taken as the Tg (°C) of the resin. The Bicerano method is described in, for example, Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0041] In step (4), the dissolution rate S3 of the resist film A in the developer A and the dissolution rate S3 of resist film C in the developer C It is preferable to prepare composition C by changing the resin content in composition B so that the difference between S3 A and S3 C The difference between S3 A The predetermined range is preferably within ±2.0%, more preferably within ±1.5%, and even more preferably within ±1.0%. If the difference in the dissolution rate of the resist film in the developer is not within the predetermined range even after changing the resin content, attempts to change the resin content can be made repeatedly until the difference falls within the predetermined range. That is, -2.0≦100×(S3 C -S3 A) / S3 A It is preferred that it is ≦2.0. The developer may be an alkaline developer or an organic developer.

[0042] The dissolution rate of the resist film in the developer can be calculated by dividing the change in the resist film thickness by the time required for processing. The time required for processing can be determined from the behavior of changes in parameters obtained by the quartz crystal microbalance (QCM) method, which are measured in real time. The specific measurement method is shown below. A resist composition is applied to a QCM electrode (a quartz crystal oscillator electrode) and baked at 120°C for 60 seconds to form a 40 nm thick resist film. This produces a QCM electrode with a resist film. The resist film is then removed by contacting the QCM electrode with the resist film with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide). During this process, the change in the frequency of the quartz crystal oscillator is monitored, and the time (T) required for the frequency change to stabilize from the start of contact with the developer is measured. The dissolution rate of the resist film (nm / sec) is calculated by dividing the thickness of the resist film before treatment (40 nm) by the measured time (T) (40 nm / T sec).

[0043] The number of moles of photodecomposable cations contained in composition A is P A , Q represented by the following formula (a) for composition A is Q A , the number of moles of photodecomposable cations contained in composition C is P C , Q represented by the following formula (a) for composition C is Q C Then, Q A / P A From Q C / P C The value obtained by subtracting A / P A It is preferable that the value is within ±0.3%, more preferably within ±0.2%, and even more preferably within ±0.1%. That is, -0.3≦100×(QA / P A -Q C / P C ) / (Q A / P A )≦0.3. Q A / P A , and Q C / P C The value of is considered to be a parameter that affects sensitivity, but by keeping this constant, it becomes easier to change the resin content, and step (4) can be completed more quickly. Q = (number of Z2 in one molecule of compound (I)) × (number of moles of compound (I)) + (number of Z3 in one molecule of compound (II)) × (number of moles of compound (II)) + (number of moles of acid diffusion controller Qb) (a) However, the acid diffusion controller Qb is a compound different from the compounds (I) and (II). The photodecomposable cation is a cation that decomposes when irradiated with actinic rays or radiation.

[0044] <Reference Resist Composition A (Composition A)> Composition A contains at least a photoacid generator and a resin.

[0045] [Photoacid generator] A photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation. Photoacid generators typically contain a photodecomposable cation. The photoacid generator is not particularly limited, but is preferably at least one of the following compounds (I) and (II): + and M2 + is preferably a photodecomposable cation. Composition A may contain at least one of compounds (I) and (II) as a photoacid generator, or may contain a photoacid generator P different from compounds (I) and (II), or may contain at least one of compounds (I) and (II) and photoacid generator P. Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which generates an acid containing a first acidic moiety derived from the structural moiety Z1 and a second acidic moiety derived from the structural moiety Z2 when irradiated with actinic rays or radiation: Structural site Z1: Anion site A1 - and cationic moiety M1 + and a structural portion that forms a first acidic site represented by HA1 upon irradiation with actinic rays or radiation. Structural site Z2: Anionic site A2 - and cationic moiety M2 + and a structural portion that forms a second acidic site represented by HA2 upon irradiation with actinic rays or radiation. However, compound (I) satisfies the following condition I. Condition I: In the compound (I), the cation moiety M1 in the structural moiety Z1 + and the cationic moiety M2 in the structural moiety Z2 + H + The compound PI in which the cationic moiety M1 in the structural moiety Z1 is replaced by + H + and the cationic moiety M2 in the structural moiety Z2. + H + and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II): A compound having two or more of the above structural moieties Z1 and one or more of the following structural moieties Z3, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety Z1 and the structural moiety Z3 when irradiated with actinic rays or radiation. Structural site Z3: a non-ionic site capable of neutralizing acids

[0046] [Compound (I)] Compound (I) is as described above. Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one first acidic moiety derived from structural moiety Z1 and one second acidic moiety derived from structural moiety Z2, compound PI corresponds to a "compound having HA1 and HA2." More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are determined by determining the acid dissociation constant of the compound PI. - The pKa at which the compound is formed is the acid dissociation constant a1, and the above "A1 - and HA2" is "A1 - and A2 - The pKa at which the compound becomes "a compound having the above formula" is the acid dissociation constant a2.

[0047] For example, when compound (I) is an acid-generating compound having two first acidic sites derived from structural moiety Z1 and one second acidic site derived from structural moiety Z2, compound PI corresponds to a "compound having two HA1s and one HA2." When the acid dissociation constant of compound PI is calculated, it is assumed that compound PI is "one A1 - and one HA1 and one HA2,” and the acid dissociation constant when “one A1 - and one HA1 and one HA2" is "a compound with two A1 - The acid dissociation constant when the compound has two A1 and one HA2 corresponds to the acid dissociation constant a1. - and one HA2" is "a compound with two A1 - and A2 - The acid dissociation constant when the compound PI becomes a compound having the cation moiety M1 in the structural moiety Z1 corresponds to the acid dissociation constant a2. + H + When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by HA1, the value of the acid dissociation constant a2 is greater than the largest value of the plurality of acid dissociation constants a1. - The acid dissociation constant when "aa" is used is a compound having one HA1 and one HA2. -When the "compound having one HA1 and one HA2" becomes the "compound having two A1s - and one HA2", when the acid dissociation constant is defined as ab, the relationship between aa and ab satisfies aa < ab.

[0048] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. Compound PI corresponds to the acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural sites Z1, the structural sites Z1 may be the same or different from each other. Also, two or more A1s - , and two or more M1s + may be the same or different from each other. In compound (I), A1 - and A2 - , and also, M1 + and M2 + may be the same or different from each other, but A1 - and A2 - are preferably different from each other.

[0049] In compound PI, the difference (absolute value) between the acid dissociation constant a1 (when there are multiple acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit value of the difference (absolute value) between the acid dissociation constant a1 (when there are multiple acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less.

[0050] In compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. As the lower limit value of the acid dissociation constant a2, -4.0 or more is preferably.

[0051] In compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. As the lower limit value of the acid dissociation constant a1, -20.0 or more is preferably.

[0052] Cationic moiety M1 + and M2 + This article explains: M1 + and M2 + is preferably an organic cation, more preferably a sulfonium cation or an iodonium cation. M1 + and M2 + The cation represented by formula (ZaI) is not particularly limited. The valence of the cation may be monovalent or divalent or higher. The cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0053] [ka]

[0054] In the above formula (ZaI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (such as butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0055] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0056] First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 is an arylsulfonium cation, in which at least one of the groups is an aryl group. The arylsulfonium cation is R 201 ~R 203 All of R may be aryl groups, or 201 ~R 203 A part of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. R 201 ~R 203 one of which is an aryl group, and R 201 ~R 203 The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-). Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0057] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation optionally has 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 more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0058] R 201 ~R 203 The substituent that the aryl group, alkyl group, and cycloalkyl group may have is preferably an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a cycloalkylalkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom (e.g., fluorine and iodine), a hydroxyl group, a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, or a phenylthio group. The above-mentioned substituent may further have a substituent if possible, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents are combined in any manner to form an acid-decomposable group.

[0059] Next, the cation (ZaI-2) will be explained. The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. R 201 ~R 203 The organic group not having an aromatic ring as the aromatic ring preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. R 201 ~R 203 are each independently 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 still more preferably a linear or branched 2-oxoalkyl group.

[0060] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), and a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl). R 201 ~R 203 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. R 201 ~R 203 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0061] Next, the cation (ZaI-3b) will be explained. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0062] [ka]

[0063] In formula (ZaI-3b), R 1c ~R5c 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. R 6c and R 7c each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. 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. R 1c ~R 7c , and R x and R y It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0064] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused 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.

[0065] R 1c ~R 5c Two or more of the following, R 6c and R7c , and R x and R y Examples of the group formed by bonding include alkylene groups such as butylene and pentylene, in which the methylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and 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.

[0066] R 1c ~R 5c , R 6c , R 7c , R x , R y , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The ring formed by bonding together may have a substituent.

[0067] Next, the cation (ZaI-4b) will be explained. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0068] [ka]

[0069] In formula (ZaI-4b), l represents an integer of 0 to 2; r represents an integer of 0 to 8; R 13represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 represents a hydroxyl group, a halogen atom (e.g., a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R 14 When a plurality of groups are present, each independently represents the above group such as a hydroxyl group. R 15 Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 may be bonded to each other to form a ring. 15 When they are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R 15 are preferably alkylene groups and bond together to form a ring structure. 15 The ring formed by bonding together may have a substituent.

[0070] In formula (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. R 13 ~R 15 , and R x and R yIt is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0071] Next, formula (ZaII) will be explained. In formula (ZaII), R 204 and R 205 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 and R 205 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0072] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 and R 205 Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include 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 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0073] Below is M1 + and M2 + Specific examples are shown below, but the present invention is not limited to these.

[0074] [ka]

[0075] [ka]

[0076] Anionic site A1 - and anionic site A2 - is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. Anionic site A1 - As the acid group, those capable of forming an acidic site with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. In addition, the anionic site A2 - As the anion moiety A1 - Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R A represents a monovalent organic group. A The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0077] [ka]

[0078] [ka]

[0079] Cationic moiety M1 + and cationic moiety M2 + is a structural moiety containing a positively charged atom or atomic group, such as a monovalent organic cation.

[0080] The specific structure of compound (I) is not particularly limited, and examples thereof include compounds represented by formulae (Ia-1) to (Ia-5) described below.

[0081] -Compound represented by formula (Ia-1)- First, the compound represented by formula (Ia-1) will be described below.

[0082] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0083] The compound represented by formula (Ia-1) can be irradiated with actinic rays or radiation to form HA. 11 -L1-A 12 It generates an acid represented by H.

[0084] In formula (Ia-1), M 11 + and M 12 + each independently represents an organic cation. A 11 - and A 12 - each independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M11 + and M 12 + may be the same or different. A 11 - and A 12 - may be the same or different, but are preferably different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + Compound PIa (HA 11 -L1-A 12 In H), A 12 The acid dissociation constant a2 derived from the acidic site represented by H is HA 11 The acid dissociation constant a1 is larger than the acid dissociation constant a1 derived from the acidic moiety represented by the formula (Ia-1). The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. The acid generated from the compound PIa and the compound represented by the formula (Ia-1) upon irradiation with actinic rays or radiation is the same. Also, M 11 + , M 12 + , A 11 - , A 12 - At least one of L1 and L2 may have an acid-decomposable group as a substituent.

[0085] In formula (Ia-1), M 11 + and M 12 + Regarding the organic cation represented by the formula M1 + and M2 + is the same as

[0086] A 11 - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1 - Also, A is intended to be a monovalent group containing 12- The monovalent anionic functional group represented by the formula (I) is the anionic moiety A2 - is intended to mean a monovalent radical comprising: A 11 - and A 12 - The monovalent anionic functional group represented by the formula (AA-1) to (AA-3) and the formula (BB-1) to (BB-6) is preferably a monovalent anionic functional group containing an anionic moiety, and more preferably a monovalent anionic functional group selected from the group consisting of the formula (AX-1) to (AX-3) and the formula (BX-1) to (BX-7). 11 - Among these, the monovalent anionic functional group represented by formula (AX-1) to (AX-3) is preferred. 12 - Of the monovalent anionic functional groups represented by formula (BX-1), a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7) is preferred, and a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-6) is more preferred.

[0087] [ka]

[0088] In formulas (AX-1) to (AX-3), R A1 and R A2 each independently represents a monovalent organic group. * represents a bonding position. R A1 The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0089] R A2 The monovalent organic group represented by the formula (I) is preferably a linear, branched, or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0090] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, and more preferably a fluorine atom, an iodine atom, or a perfluoroalkyl group.

[0091] In formulas (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * indicates the bond position. R B The monovalent organic group represented by the formula (I) is preferably a linear, branched, or cyclic alkyl group or an aryl group. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group may have a substituent. The substituent is not particularly limited, but is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. In addition, when the carbon atom serving as a bonding position in the alkyl group has a substituent, it is also preferable that the substituent is a fluorine atom or a cyano group. Here, the carbon atom serving as a bonding position in the alkyl group corresponds to, for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to -CO- specified in the formula in the alkyl group, in the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to -SO2- specified in the formula in the alkyl group, and in the case of formula (BX-6), the carbon atom directly bonded to N specified in the formula in the alkyl group. - This applies to carbon atoms directly bonded to the The alkyl group may have a carbon atom substituted with a carbonyl carbon.

[0092] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms), and more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

[0093] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (5 to 15 carbon atoms having at least one N atom, O atom, S atom, or Se atom in the ring structure), Examples of the R include a 10-membered ring, preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring, a divalent aromatic 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 even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and a divalent linking group combining two or more of these. The R is preferably a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent, for example, a halogen atom (preferably a fluorine atom).

[0094] Among these, the divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).

[0095] [ka]

[0096] In formula (L1), L 111 represents a single bond or a divalent linking group. L 111 The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -NH-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, and more preferably having a straight chain or branched chain), an optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), an optionally substituted aryl group (preferably having 6 to 10 carbon atoms), and a divalent linking group formed by combining two or more of these. The substituent is not particularly limited, and examples thereof include a halogen atom. p represents an integer of 0 to 3, and preferably an integer of 1 to 3. v represents an integer of 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. Among these, Xf1 and Xf2 are preferably each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the bond position. L in formula (Ia-1) 11 represents a divalent linking group represented by formula (L1), L in formula (L1) 111 The bond (*) on the side of the A 12 - It is preferred to combine with

[0097] -Compounds represented by formulae (Ia-2) to (Ia-4)- Next, the compounds represented by formulae (Ia-2) to (Ia-4) will be described.

[0098] [ka]

[0099] In formula (Ia-2), A 21a - and A 21b - Each independently represents a monovalent anionic functional group. 21a - and A 21b - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A is intended to be a monovalent radical containing 21a - and A 21b -The monovalent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - represents a divalent anionic functional group. 22 - The divalent anionic functional group represented by the formula (I) is the anionic moiety A2 - A divalent linking group containing 22 - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) shown below can be given.

[0100] [ka]

[0101] M 21a + , M 21b + , and M 22 + Each independently represents an organic cation. 21a + , M 21b + , and M 22 + As the organic cation represented by the formula, the above-mentioned M1 + and M2 + is the same as L 21 and L 22 each independently represents a divalent organic group.

[0102] In the above formula (Ia-2), M 21a + , M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, A is replaced by 22 The acid dissociation constant a2 derived from the acidic site represented by H is A 21aAcid dissociation constants a1-1 and A1 derived from H 21b It is larger than the acid dissociation constant a1-2 derived from the acidic site represented by H. The acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above. In addition, A 21a - and A 21b - may be the same or different. 21a + , M 21b + , and M 22 + may be the same or different from each other. M 21a + , M 21b + , M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of them may have an acid-decomposable group as a substituent.

[0103] In formula (Ia-3), A 31a - and A 32 - Each independently represents a monovalent anionic functional group. 31a - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - The same definition and preferred embodiments are also the same. A 32 - The monovalent anionic functional group represented by the above-mentioned anionic moiety A2 - A is intended to be a monovalent radical containing 32 - The monovalent anionic functional group represented by the formula (BX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - represents a divalent anionic functional group. 31b - The divalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A divalent linking group containing 31b - Examples of the divalent anionic functional group represented by formula (AX-4) include divalent anionic functional groups represented by formula (AX-4) shown below.

[0104] [ka]

[0105] M 31a + , M 31b + , and M 32 + Each independently represents a monovalent organic cation. 31a + , M 31b + , and M 32 + As the organic cation represented by the formula, the above-mentioned M1 + is the same as L 31 and L 32 each independently represents a divalent organic group.

[0106] In the above formula (Ia-3), M 31a + , M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, A is replaced by 32 The acid dissociation constant a2 derived from the acidic site represented by H is A 31a Acid dissociation constants a1-3 and A2 derived from the acidic site represented by H 31bIt is larger than the acid dissociation constant a1-4 derived from the acidic site represented by H. The acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above. In addition, A 31a - and A 32 - may be the same or different. 31a + , M 31b + , and M 32 + may be the same or different from each other. M 31a + , M 31b + , M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of them may have an acid-decomposable group as a substituent.

[0107] In formula (Ia-4), A 41a - , A 41b - , and A 42 - Each independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-2) is 21a - and A 21b - It is synonymous with A. 42 - The definition of the monovalent anionic functional group represented by A in the above formula (Ia-3) is 32 - The same definition and preferred embodiments are also the same. M 41a + , M 41b + , and M 42+ each independently represents an organic cation. L 41 represents a trivalent organic group.

[0108] In the above formula (Ia-4), M 41a + , M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, A is replaced by 42 The acid dissociation constant a2 derived from the acidic site represented by H is A 41a Acid dissociation constants a1-5 and A2 derived from the acidic site represented by H 41b It is larger than the acid dissociation constant a1-6 derived from the acidic site represented by H. The acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above. In addition, A 41a - , A 41b - , and A 42 - may be the same or different. 41a + , M 41b + , and M 42 + may be the same or different from each other. M 41a + , M 41b + , M 42 + , A 41a - , A 41b - , A 42 - , and L 41 At least one of them may have an acid-decomposable group as a substituent.

[0109] L in formula (Ia-2) 21 and L 22 and L in formula (Ia-3). 31 and L32 The divalent organic group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), a 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 even more preferably a 5- to 6-membered ring), a divalent aromatic 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 even more preferably a 5- to 6-membered ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and a divalent organic group formed by combining two or more of these. R in the above -NR- can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent, for example, a halogen atom (preferably a fluorine atom).

[0110] L in formula (Ia-2) 21 and L 22 and L in formula (Ia-3). 31 and L 32 The divalent organic group represented by the formula (L1) is preferably, for example, a divalent organic group represented by the following formula (L2).

[0111] [ka]

[0112] In formula (L2), q represents an integer of 1 to 3. * represents a bonding position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and particularly preferably both Xf are fluorine atoms.

[0113] L A represents a single bond or a divalent linking group. L A The divalent linking group represented by the formula (I) is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group formed by combining two or more of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent, for example, a halogen atom (preferably a fluorine atom).

[0114] Examples of the divalent organic group represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Ph represents a phenylene group which may have a substituent, and is preferably a 1,4-phenylene group. The substituent is not particularly limited, but is preferably an alkyl group (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkoxycarbonyl group (e.g., preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms). L in formula (Ia-2) 21 and L 22 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 21a - and A 21b - It is preferred to combine with L in formula (Ia-3) 31 and L 32 represents a divalent organic group represented by formula (L2), L in formula (L2) A The bond (*) on the side of the A 31a - and A 32 - It is preferred to combine with

[0115] -Compound represented by formula (Ia-5)- Next, formula (Ia-5) will be described.

[0116] [ka]

[0117] In formula (Ia-5), A 51a - , A 51b - , and A 51c - Each independently represents a monovalent anionic functional group. 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by the formula (I) is the anionic moiety A1 - A is intended to be a monovalent radical containing 51a - , A 51b - , and A 51c -The monovalent anionic functional group represented by the formula (AX-1) is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - represents a divalent anionic functional group. 52a - and A 52b - The divalent anionic functional group represented by the formula (I) is the anionic moiety A2 - A divalent linking group containing 52a - and A 52b - Examples of the divalent anionic functional group represented by the formula (BX-8) to (BX-11) include divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).

[0118] M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + Each independently represents an organic cation. 51a + , M 51b + , M 51c + , M 52a + , and M 52b + As the organic cation represented by the formula, the above-mentioned M1 + is the same as L 51 and L 53 L each independently represents a divalent organic group. 51 and L 53 Examples of the divalent organic group represented by the formula (Ia-2) include L 21 and L 22 The same definition and preferred embodiments are also the same. L 52represents a trivalent organic group. 52 The trivalent organic group represented by the formula (Ia-4) is L 41 The same definition and preferred embodiments are also the same.

[0119] In the above formula (Ia-5), M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, A is replaced by 52a The acid dissociation constants a2-1 and A2-1 derived from the acidic site represented by H 52b The acid dissociation constant a2-2 derived from the acidic site represented by H is A 51a Acid dissociation constant a1-1, A 51b The acid dissociation constants a1-2 and A2 are derived from the acidic sites represented by H. 51c It is larger than the acid dissociation constant a1-3 derived from the acidic site represented by H. The acid dissociation constants a1-1 to a1-3 correspond to the above-mentioned acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above-mentioned acid dissociation constant a2. In addition, A 51a - , A 51b - , and A 51c - may be the same or different. 52a - and A 52b - may be the same or different from each other. M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + may be the same or different from each other. M 51b+ , M 51c + , M 52a + , M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of them may have an acid-decomposable group as a substituent.

[0120] [Compound (II)] Compound (II) is a compound having two or more of the structural moieties Z1 and one or more of the structural moieties Z3 shown below, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety Z1 and the structural moiety Z3 when irradiated with actinic rays or radiation. Structural site Z3: a non-ionic site capable of neutralizing acids

[0121] In compound (II), the definition of the structural moiety Z1 and A1 - and M1 + The definition of the structural moiety Z1 in the compound (I) and the definition of A1 - and M1 + The definition and preferred embodiments are also the same.

[0122] In compound (II), the cationic moiety M1 in the structural moiety Z1 + H + In the compound PII, the cationic moiety M1 in the structural moiety Z1 is replaced by + H + The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by HA1 in which the acid dissociation constant a1 is substituted with HA1 is the same as the acid dissociation constant a1 in the compound PI. In addition, when compound (II) is, for example, a compound that generates an acid having two first acidic sites derived from structural site Z1 and structural site Z3, compound PII corresponds to a "compound having two HA1s." When the acid dissociation constant of this compound PII is calculated, it is considered that compound PII has "one A1 - and one HA1" and the acid dissociation constant when "a compound having one A1" - and one HA1" is "a compound with two A1 - The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0123] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties Z1 may be the same or different. - , and two or more of the above M1 + may be the same or different.

[0124] The nonionic moiety capable of neutralizing an acid in the structural moiety Z3 is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having an electron. Examples of the group capable of electrostatically interacting with a proton or the functional group having an electron include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0125] [ka]

[0126] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure, and among these, a primary to tertiary amine structure is preferred.

[0127] Compound (II) is not particularly limited, but examples thereof include compounds represented by the following formula (IIa-1) and formula (IIa-2).

[0128] [ka]

[0129] In the above formula (IIa-1), A 61a - and A 61b - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 61a + and M 61b + are the M in the above formula (Ia-1), 11 + The same definition and preferred embodiments are also the same. In the above formula (IIa-1), L 61 and L 62 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0130] In formula (IIa-1), R 2X represents a monovalent organic group. 2X The monovalent organic group represented by R is not particularly limited, and examples thereof include an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably having 3 to 15 carbon atoms), or an alkenyl group (preferably having 2 to 6 carbon atoms). 2X-CH2- contained in the alkyl group, cycloalkyl group, and alkenyl group in the monovalent organic group represented by the formula (I) may be substituted with one or a combination of two or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. The alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom (preferably a fluorine atom).

[0131] In the above formula (IIa-1), M 61a + and M 61b + The organic cation represented by H + In the compound PIIa-1, A is replaced by 61a Acid dissociation constants a1-7 and A2 derived from the acidic site represented by H 61b The acid dissociation constant a1-8 derived from the acidic site represented by H corresponds to the above-mentioned acid dissociation constant a1. In the compound (IIa-1), the cationic moiety M in the structural moiety X 61a + and M 61b + H + Compound PIIa-1, which is substituted with HA 61a -L 61 -N(R 2X )-L 62 -A 61b The compound PIIa-1 corresponds to H. The acid generated from the compound represented by formula (IIa-1) upon irradiation with actinic rays or radiation is the same as that generated from the compound PIIa-1. M 61a + , M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R 2X At least one of them may have an acid-decomposable group as a substituent.

[0132] In the above formula (IIa-2), A 71a - , A 71b - , and A 71c - are A in the above formula (Ia-1), respectively. 11 - The same definition and preferred embodiments are also the same. 71a + , M 71b + , and M 71c + are the M in the above formula (Ia-1), 11 + The same definition and preferred embodiments are also the same. In the above formula (IIa-2), L 71 , L 72 , and L 73 have the same meanings as L1 in the above formula (Ia-1), and the preferred embodiments are also the same.

[0133] In the above formula (IIa-2), M 71a + , M 71b + , and M 71c + The organic cation represented by H + In the compound PIIa-2, A is replaced by 71a Acid dissociation constant a1-9, A, derived from the acidic site represented by H 71b The acid dissociation constant a1-10 derived from the acidic site represented by H, and A 71c The acid dissociation constant a1-11 derived from the acidic site represented by H corresponds to the acid dissociation constant a1 described above. In the compound (IIa-1), the cationic moiety M in the structural moiety Z1 71a + , M 71b + , and M 71c + H + Compound PIIa-2, which is substituted with HA 71a -L 71 -N(L 73 -A 71c H)-L72 -A 71b The compound PIIa-2 corresponds to H. The acid generated from the compound represented by formula (IIa-2) upon irradiation with actinic rays or radiation is the same as that generated from the compound PIIa-2. M 71a + , M 71b + , M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 , and L 73 At least one of them may have an acid-decomposable group as a substituent.

[0134] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0135] [ka]

[0136] [ka]

[0137] Composition A may contain only compound (I) of compounds (I) and (II), or may contain only compound (II), or may contain both compound (I) and compound (II). When composition A contains compound (I), the type of compound (I) may be one type or two or more types. When composition A contains compound (II), the type of compound (II) may be one type or two or more types. The content (total content) of compounds (I) and (II) in composition A is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 5.0% by mass or more, based on the total solid content of composition A. Furthermore, the content (total content) of compounds (I) and (II) in composition A is preferably 60.0% by mass or less, more preferably 50.0% by mass or less, even more preferably 40.0% by mass or less, and particularly preferably 30.0% by mass, based on the total solid content of composition A.

[0138] [Photoacid generator P different from compounds (I) and (II)] The composition A may contain, as a photoacid generator, a photoacid generator P different from the compounds (I) and (II). The photoacid generator P typically contains a photodecomposable cation. The photoacid generator P is an anion A3 - and cation M + and generates an acid represented by HA3 upon irradiation with actinic rays or radiation. Cation M + H + The acid dissociation constant a3 derived from the acid represented by HA3, which is replaced by the cation moiety M2 in the structural moiety Z2 of the compound (I) described above, is + H + is preferably smaller than the acid dissociation constant a2 derived from the acidic site represented by HA2 in which Examples of the acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0139] M + Specific examples and preferred ranges of M1 + and M2 + is the same as

[0140] A3 -represents an anion, preferably an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0141] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkylcarboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0142] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0143] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0144] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0145] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0146] An example of the sulfonylimide anion is a saccharin anion.

[0147] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent on these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0148] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6 - ), boron fluorides (e.g., BF4 - ), and antimony fluorides (e.g., SbF6 - ) are mentioned.

[0149] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0150] [ka]

[0151] In formula (AN1), R 1 and R 2 each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a group that is not an electron-withdrawing group, such as a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonylhydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. The groups that are not electron-withdrawing groups are preferably each independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR', where R' is a monovalent hydrocarbon group.

[0152] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among them, R 1 and R 2 are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0153] L represents a divalent linking group. When a plurality of L's are present, each L may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these. Among these, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferably -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0154] L is preferably, for example, a group represented by the following formula (AN1-1). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0155] In formula (AN1-1), * a is R in formula (AN1) 3 represents the bonding position with * b is -C(R 1 )(R 2 )- represents the bonding position. X and Y each independently represent an integer of 0 to 10, and preferably an integer of 0 to 3. R 2a and R 2b each independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, there are multiple instances of R 2a and R 2b may be the same or different. However, when Y is 1 or more, -C(R 1 )(R 2 )- and CR 2b R in 2 2b is other than a fluorine atom. Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. However, X+Y in formula (AN1-1) is 1 or more, and R in formula (AN1-1) 2a and R 2bare all hydrogen atoms, Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A -SO2-* B Represents. * A is R in formula (AN1) 3 represents the bond position on the side, and * B is -SO3 in formula (AN1) - represents the bonding position on the side.

[0156] In formula (AN1), R 3 represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (e.g., an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0157] Among them, R 3 is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom), and the heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group, and among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group, which may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group obtained by removing one hydrogen atom from a ring member atom constituting the lactone structure or sultone structure in any of the structures represented by the above formulae (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) is preferred.

[0158] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0159] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0160] [ka]

[0161] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0162] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and further preferably both Xf's are fluorine atoms.

[0163] R 4 and R 5R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple 4 and R 5 may be the same or different. R 4 and R 5 The alkyl group represented by the following formula preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. R4 and R5 are preferably hydrogen atoms.

[0164] L represents a divalent linking group, and is defined as L in formula (AN1).

[0165] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0166] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, polycyclic heterocyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0167] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0168] The anion represented by formula (AN2) is SO3 - -CF2-CH2-OCO-(L) q’ -W, SO3 - -CF2-CHF-CH2-OCO-(L) q’ -W, SO3 - -CF2-COO-(L) q’ -W, SO3 - -CF2-CF2-CH2-CH2-(L) q -W or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0169] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0170] [ka]

[0171] In formula (AN3), Ar represents an aryl group (e.g., a phenyl group) and may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom or a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 or 3, and even more preferably 3.

[0172] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0173] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0174] The non-nucleophilic anion is also preferably a disulfonamide anion. Disulfonamide anions are, for example, N - (SO2-R q )2 is an anion. where R q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. q may be bonded to each other to form a ring. qThe group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0175] When composition A contains a photoacid generator P, the content of photoacid generator P is not particularly limited, but is preferably 0.1 to 50.0 mass %, more preferably 0.5 to 40.0 mass %, and even more preferably 1.0 to 30.0 mass %, relative to the total solid content of composition A.

[0176] [resin] The resin contained in composition A will be described. Composition A preferably contains an acid-decomposable resin. Hereinafter, the acid-decomposable resin may be referred to as "resin (E)." Resin (E) is a resin whose polarity increases upon the action of an acid. Resin (E) usually contains a group that decomposes under the action of acid to increase polarity (also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group. When resin (E) contains an acid-decomposable group, typically, in the pattern formation method herein, 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. As the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferred.

[0177] (Repeating unit having an acid-decomposable group) The acid-decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that is released under the action of an acid. That is, the resin (E) has a repeating unit that decomposes under the action of an acid to generate a polar group. The polarity of a resin having this repeating unit increases under the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. 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 phosphate 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, as well as alcoholic hydroxyl groups. Of these, 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.

[0178] Examples of the group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0179] In formula (Y1) and formula (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may be bonded to form a monocycle or polycycle. The alkyl groups of Rx1 to Rx3 are preferably alkyl groups having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The ring formed by combining two of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 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 tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In the cycloalkyl group formed by bonding two of Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the group represented by formula (Y1) or formula (Y2), for example, Rx1 is preferably a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is also preferable that the alkyl group, cycloalkyl group, alkenyl group, or aryl group represented by Rx1 to Rx3, and the ring formed by bonding two of Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0180] In formula (Y3), R 36 ~R 38 R each independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 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. R 36 is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a group containing a heteroatom such as an oxygen atom and / or a heteroatom such as a carbonyl group. R 38 may bond with another substituent on the main chain of the repeating unit to form a ring. 38 The group formed by bonding together the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, R 36 ~R 38 and a monovalent organic group represented by R 37 and R 38 It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0181] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0182] [ka]

[0183] 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 (for example, a group formed by combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. 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 combining these (for example, a group combining an alkyl group and a cycloalkyl group). The alkyl and cycloalkyl groups may, for example, have one methylene group replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. Preferably, 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. At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5- or 6-membered ring). From the viewpoint of pattern miniaturization, L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0184] When the actinic ray- or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, the alkyl groups, cycloalkyl groups, aryl groups, and groups combining these groups represented by L1 and L2 preferably further have a fluorine atom or an iodine atom as a substituent. The alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom or iodine atom. Specifically, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups may have, for example, one methylene group replaced with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, in the alkyl group which may contain a heteroatom, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group, the ammonium group, the mercapto group, the cyano group, the aldehyde group, and groups combining these, represented by Q, the heteroatom is preferably a heteroatom selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0185] 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 preferably an aryl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0186] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in a leaving group protecting a polar group, it is also preferable that a ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0187] Other groups that are eliminated by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0188] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0189] [ka]

[0190] 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 eliminated by the action of an acid and which may have a fluorine atom or an iodine atom, provided that at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. Examples of the divalent linking group represented by L1 which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these are linked together. Among these, L1 is preferably -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom-. The arylene group is preferably a phenylene group. 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, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0191] The alkyl group represented by R1 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by R1, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by R1 may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0192] Examples of the leaving group represented by R2 which may have a fluorine atom or an iodine atom include leaving groups represented by the above formulae (Y1) to (Y4) which have a fluorine atom or an iodine atom.

[0193] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0194] [ka]

[0195] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. 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). However, when all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0196] The alkyl group represented by Xa1, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. 11 Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0197] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and an -O-Rt- group, where Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0198] The alkyl group of Rx1 to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Rx1 to Rx3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Rx1 to Rx3 is preferably a vinyl group. The cycloalkyl group formed by combining two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Also preferred are polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. In the cycloalkyl group formed by combining two of Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. In the repeating unit represented by formula (AI), for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0199] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).The number of carbon atoms in the substituent is preferably 8 or less.

[0200] The repeating unit represented by formula (AI) is preferably an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group and T represents a single bond).

[0201] Specific examples of repeating units having an acid-decomposable group are shown below, but are not limited to these: In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0202] [ka]

[0203] The resin (E) may have, as the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond. The repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by formula (B).

[0204] [ka]

[0205] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, with the proviso that at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry1 to Ry3 may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0206] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or -CH2-R 11 Examples of such groups include groups represented by R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0207] Examples of the divalent linking group for L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group, where Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group, where Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0208] The alkyl groups Ry1 to Ry3 are preferably alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The cycloalkyl groups of Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. The aryl group of Ry1 to Ry3 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The alkenyl group of Ry1 to Ry3 is preferably a vinyl group. The alkynyl group of Ry1 to Ry3 is preferably an ethynyl group. The cycloalkenyl groups of Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, which have a structure containing a double bond in part thereof. The cycloalkyl group formed by combining two of Ry1 to Ry3 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 tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. In the cycloalkyl group or cycloalkenyl group formed by combining two of Ry1 to Ry3, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or a -SO3- group, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group. In the repeating unit represented by formula (B), for example, Ry1 is a methyl group, ethyl group, vinyl group, allyl group, or aryl group, and Ry2 and Ry3 are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0209] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms).The number of carbon atoms in the substituent is preferably 8 or less.

[0210] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).

[0211] The content of the repeating units having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (E), and the upper limit thereof is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (E).

[0212] Specific examples of repeating units having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited to these. In the formula, Xb and L1 represent any of the substituents and linking groups described above, Ar represents an aromatic group, R represents a substituent such as 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'" represents an alkyl group or a fluorinated alkyl group having 1 to 20 carbon atoms), or a carboxyl group, R' represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group or a -SO3- group, a vinylidene group, or a combination thereof, and n, m, and l represent integers of 0 or greater.

[0213] [ka]

[0214] [ka]

[0215] [ka]

[0216] The content of the repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (E), and the upper limit thereof is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units in the resin (E).

[0217] (Repeating unit having an acid group) The resin (E) may have a repeating unit having an acid group. The acid group preferably has a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the resin (E) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (E) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. When the acid group content is within the above range, development proceeds well, and the formed pattern shape is excellent, and the resolution is also excellent. The acid group is preferably, 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. In the hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Furthermore, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. 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 with a group that is cleaved by the action of an acid, and a repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0218] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (b1-1).

[0219] [ka]

[0220] In general formula (b1-1), A a1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. 21 represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are a plurality of R's, they may be the same or different. 21 When R 21 is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0221] Examples of repeating units having an acid group are shown below: In the formula, R represents a hydrogen atom or a methyl group, and a represents an integer of 1 to 3.

[0222] [ka]

[0223] [ka]

[0224] When the resin (E) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total repeating units in the resin (E), and the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (E).

[0225] The resin (E) can be synthesized by a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the resin (E) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000, as determined by GPC in terms of polystyrene. The dispersity (molecular weight distribution, Mw / Mn) of the resin (E) is preferably from 1 to 5, more preferably from 1 to 3, even more preferably from 1.2 to 3.0, and particularly preferably from 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and further the smoother the sidewalls of the resist pattern and the better the roughness.

[0226] The content of the resin (E) in the composition A is preferably from 40.0 to 99.9 mass %, more preferably from 60.0 to 90.0 mass %, based on the total solid content of the composition A. The resin (E) may be used alone or in combination of two or more kinds.

[0227] [Acid diffusion controller Qb different from compounds (I) and (II)] Composition A may contain an acid diffusion controller Qb different from compounds (I) and (II). The acid diffusion controller functions as a quencher that traps the acid generated from the photoacid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed areas caused by excess acid generated. The type of acid diffusion controller Qb is not particularly limited, and examples thereof include basic compounds (DA), low molecular weight compounds (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (DC) whose acid diffusion control ability is reduced or lost by irradiation with actinic rays or radiation. Examples of the compound (DC) include an onium salt compound (DD) that is a weak acid relative to the photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of basic compounds (DA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824. Specific examples of basic compounds (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824 and those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of low molecular weight compounds (DB) having a nitrogen atom and a group that is cleaved by the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of the onium salt compound (DD) that is a weaker acid than the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0228] In addition to the above, known compounds disclosed in, for example, U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0627] to

[0664] , U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0095] to

[0187] , U.S. Patent Application Publication No. 2016 / 0237190A1, paragraphs

[0403] to

[0423] , and U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0259] to

[0328] can be suitably used as the acid diffusion controller Qb.

[0229] When the acid diffusion controller Qb is an onium salt compound (DD) that is a weak acid relative to the photoacid generator, the acid diffusion controller Qb is an anion A4 - and cation M4 + and generates an acid represented by HA4 upon irradiation with actinic rays or radiation. Cation M4 + H + The acid dissociation constant a4 derived from the acid represented by HA4, which is replaced by the cation moiety M1 in the structural moiety Z1 of the compound (I), + H + is preferably greater than the acid dissociation constant a1 derived from the acidic site represented by HA1 in which In addition, the acid dissociation constant a4 is determined by the fact that the photoacid generator P reacts with the anion A3 - and cation M + and the acid dissociation constant a3 is preferably larger than the acid dissociation constant a3 of a compound that generates an acid represented by HA3 upon irradiation with actinic rays or radiation.

[0230] When the composition A contains an acid diffusion controller Qb, the content of the acid diffusion controller Qb is preferably 0.1 to 20.0 mass %, more preferably 1.0 to 15.0 mass %, based on the total solid content of the composition A. When the composition A contains an acid diffusion controller Qb, the acid diffusion controller Qb may be used alone or in combination of two or more kinds.

[0231] [Hydrophobic resin] Composition A may further contain a hydrophobic resin different from resin (E). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding a hydrophobic resin include control of the static and dynamic contact angle of water on the surface of the resist film and suppression of outgassing.

[0232] From the viewpoint of uneven distribution in the film surface layer, the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in a side chain portion of the resin, and more preferably has two or more of these. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin or may be substituted on the side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0233] When composition A contains a hydrophobic resin, the content of the hydrophobic resin is preferably from 0.01 to 20.0 mass %, more preferably from 0.1 to 15.0 mass %, based on the total solid content of composition A.

[0234] [Surfactants] Composition A may contain a surfactant, which can provide better adhesion and form a pattern with fewer development defects. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of fluorine-based and / or silicone-based surfactants include surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954. The surfactant may be used alone or in combination of two or more. When composition A contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass %, more preferably 0.0005 to 1.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of composition A.

[0235] [solvent] Composition A preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2). Details of the components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0236] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % relative to the total amount of the solvent.

[0237] The content of the solvent in the composition A is preferably determined so that the solid content concentration is 0.5 to 30 mass %, more preferably 1 to 20 mass %.

[0238] [Other additives] Composition A may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0239] The "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0240] <Measurement Resist Composition B (Composition B)> Composition B contains the same types of ingredients as those contained in Composition A, and is typically prepared using the same types of ingredients in the same amounts as those contained in Composition A. The components contained in composition B are the same as the components contained in composition A. In the present invention, if the measurement data obtained using composition B deviates from the reference data obtained using composition A and the deviation is not within an acceptable range, the resin content in composition B is changed in step (4) to prepare composition C so that the deviation is within the acceptable range.

[0241] [Method for forming a resist film and method for forming a resist pattern] A method for forming resist films (resist film A, resist film B, and resist film C) using resist compositions (composition A, composition B, and composition C) and a method for forming resist patterns (resist pattern A, resist pattern B, and resist pattern C) will be described. There are no particular restrictions on the procedure for forming a resist pattern (hereinafter simply referred to as a "pattern") using the resist composition, but it is preferable for the method to include the following steps. Step a: forming a resist film on a substrate using a resist composition Step b: Step of exposing the resist film Step c: developing the exposed resist film using a developer The procedures for each of the above steps will be described in detail below.

[0242] (Step a: resist film formation step) Step a is a step of forming a resist film on a substrate using a resist composition, which is composed of Composition A, Composition B, and Composition C.

[0243] An example of a method for forming a resist film on a substrate using a resist composition is a method in which the resist composition is applied onto the substrate. It is preferable to filter the resist composition before application as needed. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0244] The resist composition can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed when spinning using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After coating the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic films, organic films, anti-reflective films) may be formed under the resist film.

[0245] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, or may 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 even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0246] The thickness of the resist film (resist film A, resist film B, and resist film C) is not particularly limited, but is preferably 10 to 120 nm. When EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm. It is preferable that the resist film A, the resist film B, and the resist film C have the same thickness.

[0247] (Process b: Exposure process) Step b is a step of exposing the resist film. The exposure method may be a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably having a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams, with EUV being most preferred.

[0248] After exposure, it is preferable to perform baking (heating) before development. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds. Heating can be carried out by means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. This step is also called post-exposure baking. It is preferable that the exposure conditions for resist film A (including heating conditions if heating is performed), the exposure conditions for resist film B (including heating conditions if heating is performed), and the exposure conditions for resist film C (including heating conditions if heating is performed) are the same.

[0249] (Process c: Development process) Step c is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (also called an "organic developer").

[0250] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of the substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispense method). After the development step, a step of stopping the development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C.

[0251] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.

[0252] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0253] The developer may contain a mixture of two or more of the above solvents, or may contain water or a solvent other than the above solvents. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass, and particularly preferably substantially no water. 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, still more 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, based on the total amount of the developer.

[0254] (Other processes) The pattern formation method may include, after the step c, a step of washing with a rinse liquid.

[0255] The rinse liquid used in the rinse step after the development step using an alkaline developer is, for example, pure water, to which an appropriate amount of surfactant may be added. A suitable amount of a surfactant may be added to the rinse solution.

[0256] The rinse liquid 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 liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0257] The method for the rinsing step is not particularly limited, and examples thereof include a method in which a rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with a rinsing liquid for a certain period of time (dip method), and a method in which a rinsing liquid is sprayed onto the surface of the substrate (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern due to baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for usually 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0258] The resist composition and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0259] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0260] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as the raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0261] In addition to filtration, impurities may be removed using an adsorbent, or a combination of filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferred.

[0262] A conductive compound may be added to an organic processing liquid such as a rinse liquid to prevent breakdown of chemical piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent static discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing properties, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For example, SUS (stainless steel), or various pipes coated with antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the chemical liquid piping. Similarly, antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for the filter and O-ring.

[0263] <Method for testing resist composition> The resist composition testing method of the present invention is a resist composition testing method that includes the above-mentioned steps (1) to (4). Steps (1) to (4) are as described above. [Example]

[0264] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, processing details, and processing procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0265] The various components used in the resist compositions of the Examples and Reference Examples are shown below.

[0266] <Photoacid generator (photoacid generator X) containing at least one of compounds (I) and (II)> X-1 to X-17 were used as photoacid generators containing at least one of compounds (I) and (II). A photoacid generator containing at least one of compounds (I) and (II) is also referred to as photoacid generator X. The structural formulae of X-1 to X-17 and the values ​​of the acid dissociation constants a1 and a2 are shown below.

[0267] [ka]

[0268] [ka]

[0269] <Acid-decomposable resin (E)> As the acid-decomposable resin (E), E-1 to E-24 were used. Table 1 shows the content (mol %) of each repeating unit contained in each resin, the weight average molecular weight (Mw), and the dispersity (Mw / Mn). The content of the repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units contained in each resin. In Table 1, the content of the repeating units of each resin corresponds to the order of the repeating units in the structural formula of each resin shown below. For example, the content of the repeating unit on the left side of E-1 is 60 mol %, and the content of the repeating unit on the right side is 40 mol %. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). 13 Measurement was performed by C-NMR (nuclear magnetic resonance).

[0270] [ka]

[0271] [ka]

[0272] [ka]

[0273] [Table 1]

[0274] <Photoacid generator P> As the photoacid generators P, P-1 to P-10 were used.

[0275] [ka]

[0276] <Acid diffusion controller Qb> As the acid diffusion controller Qb, Q-1 to Q-5 were used.

[0277] [ka]

[0278] <Hydrophobic resin> As the hydrophobic resins, F-1 to F-6 shown in Table 2 below were used. Table 2 shows the type and content (mol%) of each repeating unit contained in each resin, as well as the weight average molecular weight (Mw) and dispersity (Mw / Mn). The content of each repeating unit is the ratio (molar ratio) of each repeating unit to the total repeating units contained in each resin. The type of each repeating unit is shown by the structure of the corresponding monomer. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). 13 Measurement was performed by C-NMR (nuclear magnetic resonance).

[0279] [Table 2]

[0280] The structures of the monomers ME-1 to ME-11 corresponding to the repeating units constituting the hydrophobic resins shown in Table 2 are shown below.

[0281] [ka]

[0282] <Solvent> As the solvents, G-1 to G-9 were used. G-1: Propylene glycol monomethyl ether acetate (PGMEA) G-2: Propylene glycol monomethyl ether (PGME) G-3: Propylene glycol monoethyl ether (PGEE) G-4: Cyclohexanone G-5: Cyclopentanone G-6: 2-Heptanone G-7: Ethyl lactate G-8: γ-butyrolactone G-9: Propylene carbonate

[0283] <Examples 1 to 24 and Reference Examples 1 to 24> [Process (1)] (Preparation of Reference Resist Composition A (Composition A)) The components shown in Table 3 below were mixed to obtain the content shown in Table 3 to obtain a mixed solution. The resulting mixed solution was then filtered, in this order, first through a polyethylene filter with a pore size of 50 nm, then a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, to prepare resist compositions (A-1 to A-24) with a solids concentration of 2.0 mass %. In the resist compositions, solids refer to all components other than the solvent. In Table 3, the contents (mass%) of the acid-decomposable resin (E), photoacid generator X, photoacid generator P, acid diffusion controller Qb, and hydrophobic resin refer to the mass-based content ratio relative to the total solid content of the resist composition. The mixing ratio of solvents refers to the proportion (mass ratio) of each solvent when the total solvent is taken as 100. When two or more types of each component were used, the type and content of each component were separated by a " / " symbol. For example, in resist composition A-3, "X-3 / X-8" indicates that two types of photoacid generator X, X-3 and X-8, were used, and "10.90 / 5.50" indicates that the content of X-3 was 10.90% by mass and the content of X-8 was 5.50% by mass. The resulting resist composition was used as reference resist composition A (composition A).

[0284] [Table 3]

[0285] (Formation of resist film A, exposure, development treatment, and formation of resist pattern A) An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. Composition A shown in Table 4 was applied to the underlayer film and baked at 120°C for 60 seconds to form a resist film A with a thickness of 40 nm. Using an EUV exposure device (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), pattern irradiation was performed on the silicon wafer having the obtained resist film A. As a reticle, a mask with a line size of 30 nm and a line:space ratio of 1:1 was used. After exposure, the resist film A was baked at 120°C for 60 seconds and then developed with an alkaline developer, an aqueous solution of tetramethylammonium hydroxide (2.38% by mass), to obtain a line and space pattern (resist pattern A) with a line width of 30 nm and a line:space ratio of 1:1.

[0286] (Measurement of sensitivity (standard data)) The optimum exposure dose when resolving a line-and-space pattern (resist pattern A) with a line width of 30 nm (1:1) using a critical dimension scanning electron microscope (Hitachi S-9380II) was defined as sensitivity (Eopt) (mJ / cm 2 In this way, the reference data for sensitivity was obtained.

[0287] (Measurement of LWR (reference data)) A line-and-space pattern (resist pattern A) with a line width of 30 nm (1:1) resolved at an exposure dose showing the above sensitivity (Eopt) was observed from above using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at an arbitrary point, and its standard deviation (σ) was calculated, and the measurement variation of the line width was evaluated in 3σ (nm). In this way, reference data for LWR (3σ) was obtained.

[0288] [Process (2)] (Preparation of Measurement Resist Composition B (Composition B)) Resist composition B-1 was prepared in the same manner as resist composition A-1, using the same components (different lots) in the same amounts. Furthermore, resist compositions B-2 to B-24 were prepared using the same components (different lots) in the same amounts as those used in resist compositions A-2 to A-24, respectively, using the same method. The solid content concentration of all of the resist compositions B-1 to B-24 was 2.0 mass %.

[0289] (Formation of resist film B, exposure, development treatment, and formation of resist pattern B) Formation of resist film B, exposure, development, and formation of resist pattern B were carried out in the same manner as described above (formation of resist film A, exposure, development, and formation of resist pattern A), except that composition B shown in Table 4 was used instead of composition A.

[0290] (Measurement of sensitivity (measurement data)) The sensitivity when resolving resist pattern B was determined in the same manner as the reference sensitivity data described above, and measurement data of the sensitivity was obtained.

[0291] (Measurement of LWR (measurement data)) For resist pattern B, LWR measurement data was obtained in the same manner as the LWR reference data described above.

[0292] [Process (3)] The reference data and the measured data were compared as follows to determine whether or not they were within the allowable range (acceptable).

[0293] (Sensitivity data) If the value obtained by subtracting the standard data from the measurement data is within ±0.5% of the standard data, it is considered to be within the acceptable range (pass). A The measured sensitivity data is K1 B When this is the case, -0.5≦100×(K1 B -K1 A ) / K1 A A value of ≦0.5 was considered to be within the acceptable range (passed).

[0294] (About LWR data) If the value obtained by subtracting the standard data from the measurement data is within ±2.0% of the standard data, it is considered to be within the acceptable range (pass). A The measured data of LWR is K2 B When this is the case, -2.0≦100×(K2 B -K2 A ) / K2 A A value of ≦2.0 was considered to be within the acceptable range (passed).

[0295] In all Examples and Reference Examples, step (3) was judged to be "not within the acceptable range."

[0296] [Process (4)] As described above, in all examples, the results of step (3) were judged to be "out of the acceptable range." Therefore, in all examples, step (4) was carried out as follows to prepare resist composition C (composition C). At this time, the resin content of composition A was changed to L A The resin content of composition C is L C In this case, -5.0≦100×(L C -L A ) / L A <0.0, or 0.0<100×(L C -L A ) / L A Composition C was prepared so as to satisfy the following: A resist film formed using resist composition C is also referred to as "resist film C." A resist pattern formed by exposing resist film C and developing it is also referred to as "resist pattern C." Data obtained using resist composition C is also referred to as "data C."

[0297] In Examples 1, 4 to 7, 12 to 16, and 19 to 24, the EUV absorption efficiency of the resist film was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. Details are shown below.

[0298] The EUV absorption efficiency was calculated from the A value obtained by the following formula (1). Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)

[0299] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solid content to all atoms in all solid content in the resist composition, [C] represents the molar ratio of carbon atoms derived from all solid content to all atoms in all solid content in the resist composition, [N] represents the molar ratio of nitrogen atoms derived from all solid content to all atoms in all solid content in the resist composition, [O] represents the molar ratio of oxygen atoms derived from all solid content to all atoms in all solid content in the resist composition, [F] represents the molar ratio of fluorine atoms derived from all solid content to all atoms in all solid content in the resist composition, [S] represents the molar ratio of sulfur atoms derived from all solid content to all atoms in all solid content in the resist composition, and [I] represents the molar ratio of iodine atoms derived from all solid content to all atoms in all solid content in the resist composition.

[0300] EUV absorption efficiency S1 of resist film A A and the EUV absorption efficiency S1 of the resist film C C About S1 A and S1 C The difference between S1 AThe content of the acid-decomposable resin (E) in composition B was changed so that the difference was within ±0.3% of the value of -0.3≦100×(S1 C -S1 A ) / S1 A Composition C was prepared by changing the content of the acid-decomposable resin (E) in composition B so that the ratio of the acid-decomposable resin (E) to the total weight of the composition B was ≦0.3.

[0301] In Examples 3, 17, and 18, the Tg of the resist film was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. Details are shown below.

[0302] The Tg of the resist film was calculated as the product of the “Tg of the resin” and the “content (mass %) of the resin in the solid content of the resist composition.” The “Tg of the resin” was calculated using the following method. The Tg of each homopolymer consisting of only each repeating unit contained in the resin was calculated using the Bicerano method. Hereinafter, the calculated Tg will be referred to as the "Tg of the repeating unit." Next, the mass percentage (%) of each repeating unit relative to all repeating units in the resin was calculated. Next, the Tg for each mass percentage was calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​was taken as the Tg (°C) of the resin. The Bicerano method is described in, for example, Prediction of Polymer Properties, Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method was performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0303] Glass transition temperature S2 of resist film A A and the glass transition temperature S2 of resist film C C About S2 A and S2 C The difference between S2 AThe content of the acid-decomposable resin (E) in composition B was changed so that the difference was within ±0.5% of the value of S2. C -S2 A ) / S2 A Composition C was prepared by changing the content of the acid-decomposable resin (E) in composition B so that the ratio of the acid-decomposable resin (E) to the total weight of the composition B was ≦0.5.

[0304] In Examples 2 and 8 to 11, the dissolution rate of the resist film in the developer was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. Details are shown below.

[0305] The dissolution rate of the resist film in the developer was calculated by dividing the change in the resist film thickness by the time required for processing. The time required for processing was determined from the behavior of changes in parameters obtained by the quartz crystal microbalance (QCM) method, which were measured in real time. The specific measurement method is shown below. A resist composition was applied to a QCM electrode (a quartz crystal oscillator electrode) and baked at 120°C for 60 seconds to form a 40-nm-thick resist film. This produced a QCM electrode with a resist film. The resist film was then removed by contacting the QCM electrode with the resist film with an alkaline developer (a 2.38% by mass aqueous solution of tetramethylammonium hydroxide). During this process, the change in the frequency of the quartz crystal oscillator was monitored, and the time (T) required for the frequency change to stabilize after contact with the developer was measured. The dissolution rate of the resist film (nm / sec) was calculated by dividing the thickness of the resist film before treatment (40 nm) by the measured time (T) (40 nm / T sec).

[0306] Dissolution rate S3 of resist film A in developer A and the dissolution rate S3 of resist film C in the developer C Regarding S3 A and S3 C The difference between S3 AThe content of the acid-decomposable resin (E) in composition B was changed so that the difference was within ±2.0% of the value of S3. C -S3 A ) / S3 A Composition C was prepared by changing the content of the acid-decomposable resin (E) in composition B so that the β-dispersion coefficient was ≦2.0.

[0307] Composition C-1 is a resist composition that corresponds to composition C, newly prepared by changing the content of acid-decomposable resin (E) in composition B-1, which corresponds to composition B. Similarly, compositions B-2 to B-24, which correspond to composition B, are each a resist composition that corresponds to composition C, newly prepared by changing the content of acid-decomposable resin (E). The solid content concentrations of all of the compositions C-1 to C-24 were 2.0% by mass.

[0308] In addition, in the reference example, resist composition D (also referred to as "composition D") was prepared by changing the Q / P ratio without changing the content of acid-decomposable resin (E) in composition B. P is the number of moles of photodecomposable cations contained in the resist composition, and Q is the value for the resist composition expressed by the following formula (a). Q = (number of Z2 in one molecule of compound (I)) × (number of moles of compound (I)) + (number of Z3 in one molecule of compound (II)) × (number of moles of compound (II)) + (number of moles of acid diffusion controller Qb) (a) A resist film formed using resist composition D is also referred to as "resist film D." A resist pattern formed by exposing resist film D and developing it is also referred to as "resist pattern D." Data obtained using resist composition D is also referred to as "data D."

[0309] The Q / P ratio in composition B-1, which corresponds to composition B, was changed to newly prepare a resist composition corresponding to composition D, which was designated composition D-1. Similarly, the Q / P ratio in compositions B-2 to B-24, which correspond to composition B, was changed to newly prepare resist compositions corresponding to composition D, which were designated compositions D-2 to D-24. The solid content concentrations of all of the compositions D-1 to D-24 were 2.0 mass %.

[0310] The method for determining Q / P for compositions D-2 to D-24 will be described below. First, four resist compositions were prepared using the same components (components from the same lot) used in compositions A-1 to A-24, with Q / P values ​​varying by ±5% and ±10%, and the sensitivity was evaluated in the same manner as above. A calibration curve of sensitivity versus Q / P was then created, and the Q / P values ​​were determined according to the calibration curve so that the sensitivity of compositions D-1 to D-24 would be the same as that of compositions A-1 to A-24.

[0311] In each example, 10 pieces (10 samples) were prepared in the same manner as in Example 1, except that different batches of composition B (for example, composition B-1 in Example 1) were used (the types and contents of the components were the same). For each of the prepared compositions B, a composition C was prepared by changing the content of the acid-decomposable resin (E). That is, 10 pieces each of compositions B-1 to B-24 were prepared, and 10 pieces each of compositions C-1 to C-24 were also prepared. Similarly, in each Reference Example, a composition D was prepared by changing the Q / P ratio for each of the prepared compositions B. That is, 10 pieces of each of compositions D-1 to D-24 were also prepared.

[0312] [evaluation] For Compositions C-1 to C-24 and Compositions D-1 to D-24, sensitivity data and LWR data (Data C and Data D) were obtained in the same manner as described above. As in the above, the sensitivity data was judged to be within the acceptable range (pass) if the value obtained by subtracting the reference data from Data C and Data D was within ±0.5% of the reference data. Furthermore, for the LWR data, if the value obtained by subtracting the reference data from Data C and Data D was within ±2.0% of the reference data, it was deemed to be within the acceptable range (passed). Ten each of the compositions C-1 to C-24 and compositions D-1 to D-24 were judged as to whether they passed or failed, and were evaluated according to the following criteria. A: 9-10 pass B: 7-8 pass C: 5-6 pass D: 3-4 pass E: 2 or less passes

[0313] The results are shown in Table 4 below. Table 4 lists the guidelines used when changing the content of the acid-decomposable resin (E) in each example. Table 4 also lists one example out of 10 for the content of the acid-decomposable resin (E) and Q / P for compositions C-1 to C-24 and compositions D-1 to D-24.

[0314] [Table 4]

[0315] <Examples 25 to 29 and Reference Examples 25 to 29> A mixture was obtained by mixing the components shown in Table 5 below to obtain the content shown in Table 5. The mixture was then filtered, in this order, first through a polyethylene filter with a pore size of 50 nm, then a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, to prepare resist compositions (A-25 to A-29) with a solids concentration of 2.0 mass %. The resist composition thus obtained was used as a reference resist composition A (composition A), and the above-described steps (1) to (4) were carried out, except that n-butyl acetate, an organic developer, was used instead of the alkaline developer. Resist compositions B-25 to B-29 were prepared in the same manner using the same components (different lots) as those used in resist compositions A-25 to A-29, in the same amounts. The solid content concentration of resist compositions B-25 to B-29 was all 2.0 mass %. In Examples 25, 28, and 29, the EUV absorption efficiency of the resist film was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. In Example 27, the Tg of the resist film was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. In Example 26, the dissolution rate of the resist film in the developer was determined, and using this as a guideline, the content of the acid-decomposable resin (E) in composition B was changed to prepare composition C. The content of the acid-decomposable resin (E) in compositions B-25 to B-29, which correspond to composition B, was changed to newly prepare resist compositions corresponding to composition C, which were designated compositions C-25 to C-29. The solid content concentrations of all of Compositions C-25 to C-29 were 2.0 mass %. Furthermore, the Q / P ratio in compositions B-25 to B-29, which correspond to composition B, was changed to newly prepare resist compositions corresponding to composition D, which were designated compositions D-25 to D-29. The solid content concentrations of all of the compositions D-25 to D-29 were 2.0% by mass. Sensitivity data and LWR data were obtained for Compositions C-25 to C-29 and Compositions D-25 to D-29 by the methods described above, and evaluations were carried out for Examples 25 to 29 and Reference Examples 25 to 29, respectively. The results are shown in Table 6 below.

[0316] [Table 5]

[0317] [Table 6]

[0318] The results in Tables 4 and 6 show that composition C (Examples 1 to 29), which was prepared by changing the content of acid-decomposable resin (E) in composition B, can reproduce the performance (sensitivity and LWR) of composition A with higher accuracy than composition D (Reference Examples 1 to 29), which was prepared by changing the Q / P ratio.

Claims

1. a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and an acid-decomposable resin, exposing the resist film A to light, and developing the resist film A to form a resist pattern A, thereby obtaining reference data; (2) forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A but in the same amounts as those contained in a different lot, exposing the resist film B to light, and developing the resist film B to form a resist pattern B, thereby obtaining measurement data; (3) comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a different content of the acid-decomposable resin from that of the resist composition B for measurement, if it is determined in the step (3) that the content is outside the allowable range; Including, A method for producing a resist composition, comprising carrying out at least one of the following (a) and (b) and at least one of the following (i), (ii) and (iii): (a) The reference data and the measurement data are sensitivity data, and the value obtained by subtracting the reference data from the measurement data is within ±0.5% of the reference data, which is within the tolerance range. (i) The standard data and the measurement data are line width roughness data, and the value obtained by subtracting the standard data from the measurement data is within ±2.0% of the standard data, which is considered to be within the allowable range. (i) In the step (4), a step of measuring the EUV absorption efficiency of the resist film is performed, and the content of the acid-decomposable resin in the measurement resist composition B is changed so that the difference between the EUV absorption efficiency S1A of the resist film A and the EUV absorption efficiency S1C of the resist film C formed using the resist composition C is within ±0.3% of S1A, thereby preparing the resist composition C. (ii) In the step (4), a step of measuring the glass transition temperature of the resist film is carried out, and the resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference between the glass transition temperature S2A of the resist film A and the glass transition temperature S2C of the resist film C formed using the resist composition C is within ±0.5% of S2A. (iii) In the step (4), a step of measuring the dissolution rate of the resist film in a developer is carried out, and the content of the acid-decomposable resin in the resist composition for measurement B is changed so that the difference between the dissolution rate S3A of the resist film A in a developer and the dissolution rate S3C of the resist film C formed using the resist composition C in a developer is within ±2.0% of S3A, thereby preparing the resist composition C.

2. 2. The method for producing a resist composition according to claim 1, wherein the photoacid generator comprises at least one of the following compounds (I) and (II): Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which generates an acid containing a first acidic moiety derived from the structural moiety Z1 and a second acidic moiety derived from the structural moiety Z2 when irradiated with actinic rays or radiation: Structural moiety Z1: anionic moiety A １ － and the cationic moiety M １ ＋ and HA is produced by irradiation with actinic rays or radiation. １ A structural portion forming a first acidic site represented by Structural moiety Z2: anionic moiety A ２ － and the cationic moiety M ２ ＋ and HA is produced by irradiation with actinic rays or radiation. ２ A structural portion forming a second acidic site represented by However, compound (I) satisfies the following condition I. Condition I: In the compound (I), the cationic moiety M in the structural moiety Z1 １ ＋ and the cationic moiety M in the structural moiety Z2 ２ ＋ H ＋ is a compound PI in which the cation moiety M １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Z2. ２ ＋ H ＋ HA is replaced by ２ and the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II): A compound having two or more of the structural moieties Z1 and one or more of the following structural moieties Z3, wherein the compound generates an acid containing two or more of the first acidic moieties derived from the structural moiety Z1 and the structural moiety Z3 upon irradiation with actinic rays or radiation. Structural moiety Z3: a nonionic moiety capable of neutralizing an acid

3. 3. The method for producing a resist composition according to claim 2, wherein the reference resist composition A further contains an acid diffusion controller Qb different from the compounds (I) and (II).

4. The number of moles of photodecomposable cations contained in the reference resist composition A is P Ａ , Q represented by the following formula (a) for the reference resist composition A is Q Ａ The number of moles of photodecomposable cations contained in the resist composition C is P Ｃ For the resist composition C, Q represented by the following formula (a) is replaced with Q Ｃ When this is done, Q Ａ / P Ａ From Q Ｃ / P Ｃ The value obtained by subtracting Ａ / P Ａ 4. The method for producing a resist composition according to claim 2, wherein the difference is within ±0.3% of the value of Q = (number of Z2 in one molecule of compound (I)) × (number of moles of compound (I)) + (number of Z3 in one molecule of compound (II)) × (number of moles of compound (II)) + (number of moles of acid diffusion controller Qb) (a) However, the acid diffusion controller Qb is a compound different from the compounds (I) and (II).

5. The solid content concentration of the reference resist composition A is E Ａ , the solid content concentration of the resist composition C is E Ｃ When the above E Ａ and the aforementioned E Ｃ The difference between Ａ 5. The method for producing a resist composition according to claim 1, wherein the difference is within ±2.0%.

6. The method for producing a resist composition according to any one of claims 1 to 5, wherein the light source used for the exposure is EUV.

7. a step (1) of forming a resist film A using a reference resist composition A containing a photoacid generator and an acid-decomposable resin, exposing the resist film A to light, and developing the resist film A to form a resist pattern A, thereby obtaining reference data; (2) forming a resist film B using a measurement resist composition B containing the same types of components as those contained in the reference resist composition A but in the same amounts as those contained in a different lot, exposing the resist film B to light, and developing the resist film B to form a resist pattern B, thereby obtaining measurement data; (3) comparing the reference data with the measurement data to determine whether the measurement data is within an allowable range; and a step (4) of preparing a resist composition C having a different content of the acid-decomposable resin from that of the resist composition B for measurement, if it is determined in the step (3) that the content is outside the allowable range; Including, A method for testing a resist composition, comprising: performing at least one of the following (a) and (b) and at least one of the following (i), (ii) and (iii): (a) The reference data and the measurement data are sensitivity data, and the value obtained by subtracting the reference data from the measurement data is within ±0.5% of the reference data, which is within the tolerance range. (i) The standard data and the measurement data are line width roughness data, and the value obtained by subtracting the standard data from the measurement data is within ±2.0% of the standard data, which is considered to be within the allowable range. (i) In the step (4), a step of measuring the EUV absorption efficiency of the resist film is performed, and the content of the acid-decomposable resin in the measurement resist composition B is changed so that the difference between the EUV absorption efficiency S1A of the resist film A and the EUV absorption efficiency S1C of the resist film C formed using the resist composition C is within ±0.3% of S1A, thereby preparing the resist composition C. (ii) In the step (4), a step of measuring the glass transition temperature of the resist film is carried out, and the resist composition C is prepared by changing the content of the acid-decomposable resin in the resist composition B for measurement so that the difference between the glass transition temperature S2A of the resist film A and the glass transition temperature S2C of the resist film C formed using the resist composition C is within ±0.5% of S2A. (iii) In the step (4), a step of measuring the dissolution rate of the resist film in a developer is carried out, and the content of the acid-decomposable resin in the resist composition for measurement B is changed so that the difference between the dissolution rate S3A of the resist film A in a developer and the dissolution rate S3C of the resist film C formed using the resist composition C in a developer is within ±2.0% of S3A, thereby preparing the resist composition C.

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