Method for testing a photosensitive composition and method for producing a photosensitive composition

Abstract

Provided are a method for testing a photosensitive composition and a method for producing a photosensitive composition, with which it is possible to easily test whether the photosensitive composition exhibits a predetermined LWR. This method for testing a photosensitive composition comprises: step 1, in which a resist film is formed on a substrate 1 using an acid-decomposable resin having a group that decomposes under the action of an acid to generate a polar group, and a reference photosensitive composition containing a photoacid generator, the resist film on the substrate 1 is removed using a treatment liquid, and the number of defects on the substrate 1 from which the resist film on the substrate 1 has been removed is measured to obtain reference data; step 2, in which a resist film is formed on a substrate 2 using a for-measurement photosensitive composition containing the same type of component as that contained in the reference photosensitive composition, the resist film on the substrate 2 is removed using a treatment liquid, and the number of defects on the substrate 2 from which the resist film on the substrate 2 has been removed is measured to obtain measurement data; and step 3, in which the reference data and the measurement data are compared to determine whether or not the data is within an allowable range. The treatment liquid contains a predetermined component.

Description

[Technical Field]

[0001] The present invention relates to a method for testing a photosensitive composition containing a photoacid generator and an acid-degradable resin having a group that decomposes upon the action of an acid to produce a polar group, and to a method for producing a photosensitive composition. [Background technology]

[0002] Traditionally, in the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), microfabrication using lithography with photosensitive compositions has been employed. In recent years, with the increasing integration of integrated circuits, there has been a growing demand for the formation of ultrafine patterns in the submicron or quarter-micron range. Accordingly, there has been a trend toward shorter exposure wavelengths, from the g-line to the i-line, and further to ArF excimer laser light and KrF excimer laser light. Furthermore, in addition to excimer laser light, lithography using electron beams and EUV (Extreme Ultra Violet) light is currently under development. For example, Patent Document 1 discloses a resist composition containing a photoacid generator used in photolithography using high-energy rays such as ArF excimer laser light, KrF excimer laser light, electron beams, and extreme ultraviolet light as light sources. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-126143 [Overview of the project] [Problems that the invention aims to solve]

[0004] It is desirable for photosensitive compositions to have minimal performance differences between manufacturing lots. Therefore, conventionally, when manufacturing photosensitive compositions, attempts have been made to produce photosensitive compositions that exhibit similar performance to other manufacturing lots. In such cases, to determine whether a newly manufactured photosensitive composition exhibits similar performance to a previously manufactured lot, a resist pattern was formed and its LWR (Line Width Roughness) was measured. On the other hand, measuring the LWR requires forming a resist pattern after forming a resist film, as described above. This procedure for measuring LWR is complicated, and there has been a need for a simpler method to determine whether a photosensitive composition exhibits a predetermined LWR. The object of the present invention is to provide a method for testing a photosensitive composition and a method for manufacturing a photosensitive composition that can easily determine whether or not the photosensitive composition exhibits a predetermined LWR. [Means for solving the problem]

[0005] The inventors of this invention have diligently studied the problems of the prior art and have found that the above problems can be solved by the following configuration.

[0006] (1) Step 1 involves forming a resist film on a substrate 1 using a standard photosensitive composition containing an acid-degradable resin having a group that decomposes to produce a polar group by the action of an acid, and a photoacid generator, removing the resist film on the substrate 1 using a processing solution, and measuring the number of defects on the substrate 1 from which the resist film has been removed to obtain standard data. Step 2 involves forming a resist film on a substrate 2 using a measurement photosensitive composition containing the same type of components as those in a reference photosensitive composition, removing the resist film on the substrate 2 using a processing solution, and measuring the number of defects on the substrate 2 from which the resist film has been removed to obtain measurement data. The process includes step 3, which involves comparing reference data with measurement data to determine whether it falls within an acceptable range. The treatment solution contains aromatic hydrocarbons, an organic solvent, and metal X. The aromatic hydrocarbon content is 1% by mass or less relative to the total mass of the treatment solution. The organic solvent does not contain aromatic hydrocarbons, and does contain aliphatic hydrocarbons. Metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of aromatic hydrocarbon content to metal X content is 5.0 × 10⁻⁶ 4 ~2.0×10 10 A method for testing photosensitive compositions. (2) If the measurement data falls outside the acceptable range in step 3, the method for testing a photosensitive composition according to claim 1, further comprising adjusting the components of the photosensitive composition for measurement. (3) A method for testing a photosensitive composition according to (1) or (2), wherein in step 1 and step 2, the resist film on substrate 1 and the resist film on substrate 2 are resist films that have been exposed by pattern exposure after the resist film has been formed. (4) The method for testing a photosensitive composition as described in (3), wherein the pattern exposure in step 1 and step 2 is performed using one of the following: KrF excimer laser light, ArF excimer laser light, electron beam, and extreme ultraviolet light. (5) The method for testing a photosensitive composition according to any one of (1) to (4), wherein the number of defects on substrate 1 from which the resist film has been removed and the number of defects on substrate 2 from which the resist film has been removed are measured using a defect inspection device. (6) A method for testing a photosensitive composition according to any one of (1) to (5), wherein the acid-degradable resin contains repeating units having phenolic hydroxyl groups. (7) The aliphatic hydrocarbon is undecane, A method for testing a photosensitive composition according to any one of (1) to (6), wherein the organic solvent further contains butyl acetate. (8) A method for testing the photosensitive composition described in (7), wherein the ratio of the butyl acetate content to the undecane content is 65 / 35 to 99 / 1. (9) A method for testing the photosensitive composition described in (8), wherein the ratio of the butyl acetate content to the undecane content is 90 / 10. (10) The acid-degradable resin has repeating units derived from monomers that decompose upon the action of an acid to produce polar groups, All monomers have a solubility index (R) of 2.0 to 5.0 (MPa) in the processing solution, based on the Hansen solubility parameter represented by formula (1) described later. 1 / 2 And, At least one of the monomers has a difference in solubility index (ΔR) of 4.0 (MPa) before and after acid elimination. 1 / 2 The above is a method for testing a photosensitive composition as described in any of (1) to (9). (11) In the reference data, the number of defects on substrate 1 is 0.0001 to 10 defects / cm 2 A method for testing a photosensitive composition as described in any of (1) to (10). (12) A method for testing a photosensitive composition according to any one of (1) to (11), wherein the content of aromatic hydrocarbons is 1% by mass or less with respect to the total mass of the treatment solution. (13) A method for producing a photosensitive composition, comprising a method for testing a photosensitive composition as described in any of (1) to (12). [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a method for testing a photosensitive composition and a method for manufacturing a photosensitive composition that can easily determine whether or not the photosensitive composition exhibits a predetermined LWR. [Brief explanation of the drawing]

[0008] [Figure 1] This flowchart shows a first example of a method for testing a photosensitive composition according to embodiments of the present invention. [Figure 2] This flowchart shows a first example of a method for obtaining reference data for a test method of a photosensitive composition according to an embodiment of the present invention. [Figure 3] This flowchart shows a first example of a method for acquiring measurement data for a test method of a photosensitive composition according to an embodiment of the present invention. [Figure 4] This flowchart shows a second example of a method for obtaining reference data for a test method of a photosensitive composition according to an embodiment of the present invention. [Figure 5] This flowchart shows a second example of a method for acquiring measurement data for a test method of a photosensitive composition according to an embodiment of the present invention. [Figure 6] This flowchart shows a second example of a method for testing a photosensitive composition according to an embodiment of the present invention. [Figure 7] This is a flowchart showing an example of a method for producing a photosensitive composition according to an embodiment of the present invention. [Modes for carrying out the invention]

[0009] The following describes in detail a method for testing the photosensitive composition of the present invention and a method for manufacturing the photosensitive composition, based on preferred embodiments shown in the attached drawings. The figures described below are illustrative examples for illustrating the present invention, and the present invention is not limited to the figures shown below. In the following, the "~" symbol indicating a numerical range includes the numbers written on both sides. For example, when ε is given as α ~ β, the range of ε is the range that includes both α and β, which can be expressed in mathematical notation as α ≤ ε ≤ β. Furthermore, "identical" includes the generally acceptable margin of error in the relevant technical field.

[0010] In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, the substituents are preferably monovalent. In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light such as excimer lasers, extreme ultraviolet (EUV) light, and X-rays, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0011] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M, manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0012] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described herein are those calculated using this software package.

[0013] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0014] On the other hand, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0015] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. Furthermore, as stated above, pKa refers to "pKa in aqueous solution," but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0016] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0017] The inventors have discovered that by using a predetermined processing solution on two photosensitive compositions containing the same type of component, it is possible to determine whether a photosensitive composition exhibits a level of performance that allows for identification of defects in terms of LWR performance by comparing predetermined data on the number of defects. Specifically, we found that when using a treatment solution containing aliphatic hydrocarbons and aromatic hydrocarbons / metal impurities within a specified range, there is a correlation between the difference in the number of defects and the difference in LWRs. In other words, we found that when the number of defects is similar, the performance of the LWRs is also similar, while when the number of defects is different, the performance of the LWRs also differs. When two photosensitive compositions containing the same type of component are treated with a conventional processing solution, the resulting variation in the number of defects is large, and the variation in the LWR result is also large. In contrast, when the processing solution of the present invention was used on two photosensitive compositions containing the same type of component, the range of variation in the number of defects and the range of variation in the LWR were both small, and when comparing the results of the number of defects, it was found that the LWR also showed a similar level of performance. The following provides a detailed explanation of the testing method for photosensitive compositions.

[0018] [Example of a method for testing photosensitive compositions] Figure 1 is a flowchart showing a first example of a method for testing a photosensitive composition according to an embodiment of the present invention. Figure 2 is a flowchart showing a first example of a method for obtaining reference data according to a method for testing a photosensitive composition according to an embodiment of the present invention, and Figure 3 is a flowchart showing a first example of a method for obtaining measurement data according to a method for testing a photosensitive composition according to an embodiment of the present invention.

[0019] A first example of a method for testing a photosensitive composition, as shown in Figure 1, includes a step 1 (step S10) for acquiring reference data, a step 2 (step S12) for acquiring measurement data, and a step 3 (step S14) for comparing the reference data and the measurement data to determine whether they are within an acceptable range. In step 3 (step S14), if the result is within an acceptable range, it is determined to be a photosensitive composition exhibiting a predetermined LWR. On the other hand, if the result falls outside the acceptable range in step 3 (step S14), the photosensitive composition is determined not to exhibit a predetermined LWR. Thus, in the method for assaying a photosensitive composition, it is possible to easily assay whether the photosensitive composition exhibits a predetermined LWR (Line Width Roughness).

[0020] The step 1 (step S10) of obtaining reference data has the steps shown below. The step 1 (step S10) shown in FIG. 2 forms a resist film on a substrate using a reference photosensitive composition containing an acid-decomposable resin having a group that decomposes by the action of an acid to generate a polar group and a photoacid generator (step S20). The substrate is not particularly limited, and a semiconductor substrate such as a silicon substrate is used. The substrate is preferably washed in advance and foreign substances on the substrate are removed. There is no limit to the size of foreign substances on the substrate, and examples include those of 20 nm or more. The method for forming the resist film is not particularly limited, and for example, it is formed using a spin coater. In forming the resist film, after applying the reference photosensitive composition on the substrate, a pre-bake treatment may be performed on the coating film of the reference photosensitive composition. Next, the resist film on the substrate is removed using a treatment liquid (step S22). The method for removing the resist film is not particularly limited as long as a treatment liquid is used. The treatment liquid may be atomized and applied to the resist film for removal, or the resist film may be immersed in the treatment liquid for removal. Regarding various materials used in this step, details will be described later.

[0021] Next, the number of defects on the substrate from which the resist film has been removed is measured using, for example, a defect inspection device (step S24). The number of defects is measured to obtain reference data (step S10). In the reference data, the number of defects may be the total number of defects on the substrate, or the value obtained by dividing the number of defects by the surface area of the substrate, that is, the number of defects per unit area may be used as the reference data. In this case, the reference data is represented by, for example, pieces / cm 2 For example, the number of defects is preferably 0.0001 to 10 pieces / cm 2 and more preferably 0.0005 to 5 pieces / cm 2More preferably, 0.001 to 1 piece / cm 2 That is even more preferable. Here, defects on the substrate after the resist film has been removed refer to foreign matter such as particles and residues remaining on the substrate. These defect-causing components are mainly contained in the resist film. More specifically, when a resist film is formed on the substrate, components in the resist film that can become defects are adsorbed onto the substrate, and even after the resist film is removed with a processing solution, these components remain on the substrate, resulting in defects. Furthermore, while the number of defects can be measured using publicly known methods, for example, the number of defects can be measured using UVision5 (manufactured by AMAT).

[0022] Step 2 (Step S12) for acquiring measurement data includes the following steps. Step 2 (Step S12) shown in Figure 3 involves forming a resist film on a substrate using a measurement photosensitive composition containing the same types of components as those included in the reference photosensitive composition (Step S30). The substrate is as described in step S20 above. The method for forming the resist film is as described in step S20 above. Next, the resist film on the substrate is removed using a processing solution (step S32). The resist film is removed in the same manner as in step S22 described above. Next, the number of defects on the substrate from which the resist film has been removed is measured using a defect inspection device (step S34). The number of defects is measured in the same manner as in step S24. Using the method described above, the number of defects is measured and measurement data is obtained (step S12). The measurement data may be the same as the reference data: the number of defects may be the total number of defects on the substrate, or it may be the number of defects divided by the area on the substrate, i.e., the number of defects per unit area. In this case, the measurement data may be, for example, pieces / cm 2 It is represented as follows.

[0023] In step S14 (process 3), the reference data and the measured data are made to be in the same data format in order to compare them. By making the data format the same, they can be easily compared. As described above, in step S14 (process 3), the reference data and the measured data are compared to determine whether they are within the acceptable range. The acceptable range is set appropriately depending on the application, for example. The acceptable range is defined by a ratio γ, which is expressed as (measured data) / (reference data). For example, the ratio γ is 0.9 ≤ γ ≤ 1.1. In addition to the above ratio γ, the acceptable range can also be set to be within (reference data) ± (an arbitrary reference range set from past measurement results, etc.).

[0024] Figure 4 is a flowchart showing a second example of a method for obtaining reference data for the photosensitive composition testing method according to an embodiment of the present invention, and Figure 5 is a flowchart showing a second example of a method for obtaining measurement data for the photosensitive composition testing method according to an embodiment of the present invention. Note that in Figures 4 and 5, detailed explanations of the same processes as in Figures 2 and 3 are omitted. The second example of the method for acquiring reference data and the second example of the method for acquiring measurement data differ from the first example of the method for acquiring reference data and the first example of the method for acquiring measurement data described above in that the resist film is pattern-exposed.

[0025] In the second example of the method for acquiring reference data, as shown in Figure 4, after forming the resist film (step S20), the resist film is subjected to pattern exposure (step S21). After step S21, the resist film is removed (step S22). Subsequently, the number of defects on the substrate from which the resist film has been removed is measured using a defect inspection device (step S24), and reference data is acquired (step S10). In the second example of the method for acquiring measurement data, as shown in Figure 5, after forming the resist film (step S30), the resist film is subjected to pattern exposure (step S31). After step S31, the resist film is removed (step S32). Subsequently, the number of defects on the substrate from which the resist film has been removed is measured using a defect inspection device (step S34), and measurement data is acquired (step S12). In this way, reference data and measurement data can also be obtained by applying pattern exposure to the resist film.

[0026] In step S21 and step S31, it is preferable that the exposure pattern and exposure conditions are the same. Furthermore, the pattern exposure is performed with light of a wavelength appropriate to the photosensitive composition. For example, one of the following can be used: KrF excimer laser light, ArF excimer laser light, electron beam, or extreme ultraviolet (EUV). The pattern exposure in steps S21 and S31 is not particularly limited and may be, for example, an isolated resist pattern, a dot pattern, or a line and space pattern. When the photosensitive composition is of the positive type, the pattern used for pattern exposure is a pattern such as holes and trenches, where the exposed areas disappear upon development. When the photosensitive composition is of the negative type, the pattern used for pattern exposure is a pattern such as dots and lines, where the exposed areas remain after development.

[0027] [Second example of a method for testing photosensitive compositions] Figure 6 is a flowchart showing a second example of a method for testing a photosensitive composition according to an embodiment of the present invention. In the second example of the method for testing a photosensitive composition shown in Figure 6, a detailed explanation of the steps which are the same as those in the first example of the method for testing a photosensitive composition described above will be omitted. The second example of the method for testing a photosensitive composition differs from the first example of the method for testing a photosensitive composition described above in that, in step S14 (step 3), if the measurement data falls outside the acceptable range when comparing the reference data with the measurement data, the components of the photosensitive composition for measurement are adjusted (step S16). On the other hand, in step S14 (process 3), if the measurement data is within an acceptable range, no component adjustment is performed. In addition, in step S14 (step 3), the adjustment of the components of the photosensitive composition for measurement (step S16) may be repeated until the measurement data falls within an acceptable range. The photosensitive composition for measurement contains the same components as those contained in the reference photosensitive composition. When adjusting the components of the photosensitive composition for measurement in step S16, for example, the amount of at least one of the photoacid generator and the acid-degradable resin is adjusted. When comparing the measurement data with the reference data, if the measurement data is greater than or less than the reference data, etc., the components to be adjusted and the amount of adjustment may be predetermined during component adjustment, depending on the difference between the measurement data and the reference data and the degree of the difference between the measurement data and the reference data.

[0028] [An example of a method for producing a photosensitive composition] Figure 7 is a flowchart showing an example of a method for manufacturing a photosensitive composition according to an embodiment of the present invention. The above-described method for testing the photosensitive composition can be used in the method for manufacturing the photosensitive composition. In the method for manufacturing the photosensitive composition shown in Figure 7, a detailed explanation of the steps identical to those in the first example of the method for testing the photosensitive composition described above will be omitted. The method for manufacturing a photosensitive composition differs from the first example of the method for testing a photosensitive composition in the following respects. In the method for manufacturing a photosensitive composition, step S14 (step 3) includes a step (step S40) in which, when the measurement data is within an acceptable range when the reference data is compared with the measurement data, the photosensitive composition for measurement is deemed acceptable. The acceptable product is then made into a photosensitive composition product. On the other hand, in step S14 (step 3), if the measurement data falls outside the acceptable range when comparing the reference data with the measurement data, the photosensitive composition for measurement is deemed unacceptable (step S42). The unacceptable product is not included in the final product.

[0029] In the method for manufacturing the photosensitive composition, if a photosensitive composition for measurement is deemed unsuitable (step S42), the components of the photosensitive composition for measurement may be adjusted (step S44). The component adjustment of the photosensitive composition for measurement (step S44) is the same process as the component adjustment of the photosensitive composition for measurement (step S16) in the second example of the method for testing the photosensitive composition described above, so a detailed explanation is omitted. In the method for manufacturing the photosensitive composition, the component adjustment of the photosensitive composition for measurement (step S16) may be repeated until the measurement data falls within an acceptable range.

[0030] In the above explanation, comparison and judgment are performed, for example, by inputting various numerical values ​​into a computer, comparing them with acceptable ranges, and making a judgment based on those acceptable ranges. Thus, comparison and judgment are performed, for example, by a computer.

[0031] The present invention is basically configured as described above. Although the method for testing a photosensitive composition and the method for manufacturing a photosensitive composition of the present invention have been described in detail above, the present invention is not limited to the embodiments described above, and various improvements or modifications may be made without departing from the spirit of the present invention. The materials used in the above testing method are described in detail below.

[0032] [Processing solution] The treatment solution contains aromatic hydrocarbons, an organic solvent other than aromatic hydrocarbons, and metal X, wherein the organic solvent contains aliphatic hydrocarbons, and metal X is at least one metal selected from the group consisting of Al, Fe, and Ni, and the mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10⁻⁶. 4 ~2.0×10 10 That is the case. The components contained in the treatment solution are described in detail below.

[0033] <Aromatic hydrocarbons> The treatment solution contains aromatic hydrocarbons. "Aromatic hydrocarbons" refer to hydrocarbons that consist only of hydrogen and carbon atoms and have an aromatic ring. Aromatic hydrocarbons are not included in organic solvents. The aromatic hydrocarbon content is preferably 1% by mass or less, more preferably 1 to 10,000 ppm by mass, even more preferably 5 to 10,000 ppm by mass, and particularly preferably 50 to 10,000 ppm by mass, relative to the total mass of the treatment solution. If the aromatic hydrocarbon contains two or more types of aromatic hydrocarbons, it is preferable that the total content of these two or more aromatic hydrocarbons is within the above range.

[0034] The number of carbon atoms in the aromatic hydrocarbon is preferably 6 to 30, more preferably 6 to 20, and even more preferably 10 to 12. The aromatic rings in aromatic hydrocarbons may be monocyclic or polycyclic. The number of members in the aromatic ring of an aromatic hydrocarbon is preferably 6 to 12, more preferably 6 to 8, and even more preferably 6. The aromatic ring of the aromatic hydrocarbon may have further substituents. Examples of substituents include alkyl groups, alkenyl groups, and groups combining them. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. Examples of aromatic rings in aromatic hydrocarbons include optionally substituted benzene rings, optionally substituted naphthalene rings, and optionally substituted anthracene rings, with optionally substituted benzene rings being preferred. In other words, benzene, which may have substituents, is preferred as the aromatic hydrocarbon.

[0035] Aromatic hydrocarbons are C 10 H 14 , C 11 H16 and C 10 H 12 Preferably, it includes at least one selected from the group consisting of the following: Furthermore, as aromatic hydrocarbons, compounds represented by formula (c) are also preferred.

[0036] [ka]

[0037] In formula (c), R c represents a substituent. c represents an integer from 0 to 6.

[0038] R c represents a substituent. R c The substituents represented are preferably alkyl groups or alkenyl groups. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. R c If there are multiple instances, R c They may be the same or different, R c These elements may join together to form a ring. Also, R c (R c If multiple R c A part or all of () and the benzene ring in formula (c) may condense to form a fused ring.

[0039] c represents an integer between 0 and 6. c is preferably an integer between 1 and 5, and more preferably an integer between 1 and 4.

[0040] The molecular weight of the aromatic hydrocarbon is preferably 50 or more, more preferably 100 or more, and even more preferably 120 or more. The upper limit is preferably 1000 or less, more preferably 300 or less, and even more preferably 150 or less.

[0041] Examples of aromatic hydrocarbons include C1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, and 1-ethyl-2,4-dimethyl-benzene. 10 H 14 ;C such as 1-methyl-4-(1-methylpropyl)-benzene and (1-methylbutyl)-benzene 11 H 16 ;C such as 1-methyl-2-(2-propenyl)-benzene and 1,2,3,4-tetrahydro-naphthalene 10 H 12 These are some examples. Aromatic hydrocarbons include 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-methyl-4-(1-methylpropyl)-benzene, and C 10 H 12 Preferably, 1-ethyl-3,5-dimethylbenzene or 1,2,3,5-tetramethylbenzene is more preferred.

[0042] Aromatic hydrocarbons may be used individually or in combination of two or more. The treatment solution preferably contains two or more aromatic hydrocarbons, more preferably three or more aromatic hydrocarbons, even more preferably three to eight aromatic hydrocarbons, and particularly preferably three to four aromatic hydrocarbons. One example of a method for measuring the content of aromatic hydrocarbons is the method for measuring the content of organic solvents, which will be described later. Methods for adjusting the aromatic hydrocarbon content include, for example, selecting raw materials with a low aromatic hydrocarbon content as constituent materials for various components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding aromatic hydrocarbons.

[0043] <Organic solvents> The treatment solution contains organic solvents other than the aromatic hydrocarbons mentioned above. In other words, aromatic hydrocarbons are not included in the above organic solvents in this specification.

[0044] ≪Aliphatic hydrocarbons≫ Organic solvents include aliphatic hydrocarbons. "Aliphatic hydrocarbons" refer to hydrocarbons that consist only of hydrogen and carbon atoms and do not have an aromatic ring. Aliphatic hydrocarbons may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. Furthermore, the aliphatic hydrocarbons may be either saturated or unsaturated. Aliphatic hydrocarbons often have two or more carbon atoms, preferably five or more, and more preferably ten or more. The upper limit is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 13 or less. Specifically, the number of carbon atoms in the aliphatic hydrocarbon is preferably 11.

[0045] Examples of aliphatic hydrocarbons include pentane, isopentane, hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, isooctane, nonane, decane, methyldecane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepradecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane. The aliphatic hydrocarbon preferably contains an aliphatic hydrocarbon having 5 or more carbon atoms (preferably 20 or fewer carbon atoms), more preferably contains an aliphatic hydrocarbon having 10 or more carbon atoms (preferably 13 or fewer carbon atoms), even more preferably contains at least one selected from the group consisting of decane, undecane, dodecane, and methyldecane, and particularly preferably contains undecane.

[0046] The aliphatic hydrocarbon content is preferably 0.8% by mass or more and less than 100% by mass, more preferably 1 to 50% by mass, even more preferably 3 to 30% by mass, and particularly preferably 8 to 18% by mass, based on the total mass of the treatment solution. The aliphatic hydrocarbon content is preferably 0.8% to 100% by mass, more preferably 1 to 100% by mass, even more preferably 2 to 100% by mass, even more preferably 2 to 50% by mass, particularly preferably 3 to 30% by mass, and most preferably 8 to 18% by mass, relative to the total mass of the organic solvent.

[0047] Ester-based solvents The organic solvent preferably further contains an ester-based solvent. The ester solvent may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. The number of carbon atoms in ester solvents is often 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The upper limit is often 20 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less. Specifically, the number of carbon atoms in the ester solvent is preferably 6.

[0048] Examples of ester solvents include butyl acetate, isobutyl acetate, tertbutyl acetate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, hexyl acetate, methoxybutyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, amyl formate, isoamyl formate, methyl lactate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, ethyl butyrate, ethyl isobutyrate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, and isobutyl propionate. The ester solvent preferably contains at least one selected from the group consisting of butyl acetate, isobutyl acetate, amyl formate, ethyl acetate, and hexyl acetate, more preferably contains at least one selected from the group consisting of butyl acetate, isobutyl acetate, ethyl acetate, and hexyl acetate, and even more preferably contains butyl acetate.

[0049] The content of the ester solvent is preferably 10% by mass or more and less than 100% by mass, more preferably 60-99% by mass, even more preferably 60-95% by mass, and particularly preferably 80-90% by mass, based on the total mass of the treatment solution. The content of the ester solvent is preferably 10% by mass or more and less than 100% by mass, more preferably 60-99% by mass, even more preferably 60-95% by mass, and particularly preferably 80-90% by mass, relative to the total mass of the organic solvent.

[0050] The organic solvent preferably contains an aliphatic hydrocarbon and an ester solvent, and more preferably consists only of an aliphatic hydrocarbon and an ester solvent. The aliphatic hydrocarbon preferably contains at least one selected from the group consisting of undecane, dodecane, and decane, and the ester solvent preferably contains at least one selected from the group consisting of butyl acetate, isobutyl acetate, amyl formate, ethyl acetate, and hexyl acetate. In particular, the organic solvent preferably consists only of undecane and butyl acetate. When the organic solvent contains aliphatic hydrocarbons and ester solvents, the ratio of the ester solvent content to the aliphatic hydrocarbon content (ester solvent content / aliphatic hydrocarbon content) is preferably 65 / 35 to 99 / 1, more preferably 85 / 15 to 95 / 5, and even more preferably 90 / 10. The total content of aliphatic hydrocarbons and ester solvents is preferably 10% by mass or more and less than 100% by mass, more preferably 80% by mass or more and less than 100% by mass, and even more preferably 95% by mass or more and less than 100% by mass, based on the total mass of the treatment solution. The total content of aliphatic hydrocarbons and ester solvents is preferably 10 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 95 to 100% by mass, and particularly preferably 99 to 100% by mass, relative to the total mass of the organic solvent.

[0051] <<Other Solvents>> The organic solvent may contain other solvents in addition to those listed above. Other solvents include, for example, ketone-based solvents, amide-based solvents, and ether-based solvents.

[0052] Organic solvents may be used individually or in combination of two or more types. The organic solvent content is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total mass of the treatment solution. The upper limit is often less than 100% by mass, based on the total mass of the treatment solution. Methods for measuring the content of organic solvents include, for example, using GC (gas chromatography) and GC-MS (gas chromatography-mass spectrometry).

[0053] <Metal X> The processing solution contains metal X. Metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. Preferably, the treatment solution contains all of the metals Al, Fe, and Ni. The above-mentioned metal X may exist in an ionic state in the processing solution, or it may exist in a zero-valent state. If it exists in a zero-valent state, it may exist in particulate form.

[0054] Metal X may be used alone or in combination of two or more types. The content of metal X is preferably 0.01 to 3000 ppt by mass, more preferably 0.1 to 2500 ppt by mass, and even more preferably 0.1 to 2000 ppt by mass, relative to the total mass of the treatment solution. If the treatment solution contains two or more metals, it is preferable that the total content of the two or more metals falls within the above range. Furthermore, it is preferable that the content of at least one of Al, Fe, and Ni in metal X is 0.1 to 2000 ppt by mass relative to the total mass of the treatment solution.

[0055] The mass ratio of aromatic hydrocarbon content to metal X content (aromatic hydrocarbon content / metal X content) is 5.0 × 10⁻⁶ 4 ~2.0×10 10 Therefore, 3.0 × 10 5 ~1.0×10 9 Preferably, 3.0 × 105 ~2.5×10 8 This is preferable. Examples of known methods for measuring the content of metal X include ICP-MS (ICP mass spectrometry). Methods for adjusting the content of metal X include, for example, filtering using the above-mentioned filter, selecting raw materials with a low content of metal X as raw materials constituting various components, distilling under conditions that suppress contamination by lining the inside of the apparatus with Teflon®, and adding metal X or a compound containing metal X.

[0056] [Reference photosensitive composition, photosensitive composition for measurement] The standard photosensitive composition includes an acid-degradable resin having a group that decomposes upon the action of an acid to produce a polar group, and a photoacid generator. Furthermore, the photosensitive composition for measurement contains the same types of components as the reference photosensitive composition described above. Containing the same types of components means containing components with the same structure, although their content may differ. Regarding resins containing repeating units, it is sufficient that the types constituting the repeating units are the same, and the content of each repeating unit may differ. More specifically, with respect to acid-degradable resins, it is sufficient that the type of repeating unit in the acid-degradable resin contained in the reference photosensitive composition is the same as the type of repeating unit in the acid-degradable resin contained in the measurement photosensitive composition, but the content of each repeating unit in the acid-degradable resin contained in the reference photosensitive composition may be different from the content of each repeating unit in the acid-degradable resin contained in the measurement photosensitive composition. Furthermore, the content of the acid-degradable resin contained in the reference photosensitive composition may be different from the content of the acid-degradable resin contained in the measurement photosensitive composition. Furthermore, with respect to the photoacid generator, it is sufficient that the photoacid generator contained in the reference photosensitive composition and the photoacid generator contained in the measurement photosensitive composition are compounds with the same structure, and the content of the photoacid generator contained in the reference photosensitive composition and the content of the photoacid generator contained in the measurement photosensitive composition may be different. Therefore, for example, if the reference photosensitive composition contains a photoacid generator X and an acid-degradable resin containing specific repeating units A and B, the measurement photosensitive composition will also contain a photoacid generator X and an acid-degradable resin containing specific repeating units A and B. Furthermore, if the reference photosensitive composition contains other components besides the photoacid generator and the acid-degradable resin, the measurement photosensitive composition also contains other components of the same type (e.g., an acid diffusion control agent). For example, if the reference photosensitive composition contains an acid diffusion control agent Z, the measurement photosensitive composition also contains an acid diffusion control agent Z having the same structure as the acid diffusion control agent Z contained in the reference photosensitive composition, although the content may differ. In addition, if a resin containing repeating units is used as another component, similar to the acid-degradable resin described above, it is sufficient that the type of repeating units in the resin contained in the measurement photosensitive composition is the same as the type of repeating units in the resin contained in the reference photosensitive composition, although the content of the repeating units and the content of the resin may differ. It should be noted that the photosensitive composition used for measurement is often a different batch of composition, manufactured at a different time than the reference photosensitive composition. The following provides a detailed description of each component.

[0057] <An acid-degradable resin containing a group that decomposes under the action of acid to produce a polar group> The standard photosensitive composition contains an acid-degradable resin (hereinafter also simply referred to as "resin (A)") which has a group that decomposes upon the action of an acid to produce a polar group (hereinafter also simply referred to as "acid-degradable group"). Details of acid-degradable resins will be described in more detail later, but one preferred embodiment of an acid-degradable resin is one in which the acid-degradable resin has repeating units derived from monomers that decompose upon the action of acid to produce polar groups, and all of the above monomers are represented by formula (1) described later, and have a solubility index (R) based on the Hansen solubility parameter in the treatment solution of 2.0 to 5.0 (MPa).1 / 2 Furthermore, at least one of the monomers has a difference (ΔR) of solubility index (R) before and after acid elimination of 4.0 (MPa). 1 / 2 The above are examples of the embodiments described above. Below, we will first explain the above characteristics.

[0058] Hansen solubility parameters can be used as one example to identify resins with desired properties. The Hansen solubility parameter divides the solubility of a substance into three components (dispersion term δd, polarity term δp, and hydrogen bonding term δh) and represents them in three-dimensional space. The dispersion term δd represents the effect of dispersion forces, the polarity term δp represents the effect of inter-dipole forces, and the hydrogen bonding term δh represents the effect of hydrogen bonding forces. The definition and calculation of Hansen solubility parameters are described in Charles M. Hansen's *Hansen Solubility Parameters: A Users Handbook* (CRC Press, 2007). Furthermore, by using the computer software *Hansen Solubility Parameters in Practice* (HSPiP), Hansen solubility parameters can be easily estimated from the chemical structure of compounds for which literature values ​​are unknown. In this invention, using HSPiP version 4.1, the estimated values ​​are used to determine the dispersion term δd, polarity term δp, and hydrogen bonding term δh of the monomer. For solvents and monomers registered in the database, those values ​​are used.

[0059] Generally, the Hansen solubility parameter of a monomer constituting a particular resin can be determined by a solubility test, in which a sample of the monomer constituting the resin is dissolved in a number of different solvents for which the Hansen solubility parameter has been established, and the solubility is measured. Specifically, among the solvents used in the above solubility test, a sphere (solubility sphere) is found such that all the points in three dimensions of the solvent in which the monomer constituting the resin is dissolved are contained inside the sphere, and the points of the solvent in which the monomer is not dissolved are outside the sphere. The coordinates of the center of this sphere are taken as the Hansen solubility parameter of the monomer constituting the resin. For example, if the Hansen solubility parameter of a different solvent that was not used to measure the Hansen solubility parameter of the monomer constituting the resin is (δd, δp, δh), then if the point indicated by that coordinate is contained within the solubility sphere of the monomer constituting the resin, then that solvent is considered to dissolve the monomer constituting the resin. On the other hand, if that coordinate point is outside the solubility sphere of the monomer constituting the resin, then this solvent is considered not to be able to dissolve the monomer constituting the resin.

[0060] In the present invention, by utilizing the above Hansen solubility parameter, a resin (A) consisting of such structural units can be used, with the treatment solution as a reference, that is, with the coordinate which is the Hansen solubility parameter of the treatment solution as a reference, such that structural units (or monomers) located at a certain distance from that coordinate dissolve appropriately in the treatment solution. In other words, the dispersion term of the Hansen solubility parameter of the processed liquid is δd2(MPa) 1 / 2 , the polarity term is δp2(MPa) 1 / 2 and the hydrogen bonding term is δh2(MPa) 1 / 2 Based on the Hansen solubility parameter, the dissolution parameter distance R from the treatment solution, shown in equation (1), is used as the dissolution index for each monomer that induces the structural units constituting the resin (hereinafter, this may be referred to as the dissolution index (R)). Equation (1) R = (4(δd1 - δd2) 2 +(δp1-δp2) 2 +(δh1―δh2) 2 ) 1 / 2 δd1 represents the dispersion term in the Hansen solubility parameter of the above monomer. δp1 represents the polarity term in the Hansen solubility parameter of the above monomer. δh1 represents the hydrogen bonding term in the Hansen solubility parameter of the above monomer. δd2 represents the dispersion term in the Hansen solubility parameter of the above-mentioned treatment solution. δp2 represents the polarity term in the Hansen solubility parameter of the above-mentioned treatment solution. δh2 represents the hydrogen bonding term in the Hansen solubility parameter of the above-mentioned treatment solution. The δd2, δp2, or δh2 of the treatment solution are determined by multiplying the δd2, δp2, or δh2 of the solvent components (e.g., aromatic hydrocarbons, organic solvents) contained in the treatment solution by the content of the solvent components and summing the results.

[0061] In resin (A), all monomers that decompose upon the action of acid to produce polar groups have a solubility index (R) of 2.0 to 5.0 (MPa). 1 / 2 Preferably, the pressure is 3.1 to 4.9 (MPa). 1 / 2 It is more preferable that the pressure be 3.2 to 4.9 (MPa). 1 / 2 It is even more preferable that this be the case. At least one structural unit contained in resin (A) has a difference in dissolution index (R) before and after acid desorption (difference in dissolution index (△R)) of 4.0 (MPa). 1 / 2 It is preferable that the structural unit is derived from a monomer having a group that decomposes to form a polar group under the action of the above-mentioned acids. There is no particular upper limit to the above ΔR, but 10 (MPa) 1 / 2 The following are common cases.

[0062] The following details the repeating units contained in acid-degradable resins.

[0063] ≪Repeating units with acid-degradable groups (Aa)≫ The resin (A) preferably has repeating units (Aa) (hereinafter also referred to as "repeating units (Aa)") which have groups that decompose upon the action of an acid to produce polar groups. An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a leaving group that is removed upon the action of an acid. Resins having repeating units (Aa) become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents.

[0064] Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0065] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (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)

[0066] In formulas (Y1) and (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 combine to form a monocycle or polycycle. Preferred alkyl groups for Rx1 to Rx3 are C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Preferred cycloalkyl groups for Rx1 to Rx3 are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two 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 a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having 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 by vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. When the reference photosensitive composition and the photosensitive composition for measurement are, for example, EUV exposure resist compositions, it is also preferable that the alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups represented by Rx1 to Rx3, and the rings formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0067] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. Furthermore, in the repeating unit having an acid-degradable group, R 38 It may bond with other substituents on the repeating main chain to form a ring. 38The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the reference photosensitive composition and the measurement photosensitive composition are, for example, EUV exposure resist compositions, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0068] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0069] [ka]

[0070] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group 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 which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group having 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 joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl or adamantane groups.

[0071] When the reference photosensitive composition and the measurement photosensitive composition are, for example, EUV exposure resist compositions, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms (that is, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group). Furthermore, when the reference photosensitive composition and the photosensitive composition for measurement are, for example, EUV exposure resist compositions, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain a heteroatom, and the aldehyde group which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom, an iodine atom which may contain an oxygen atom.

[0072] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group. When the reference photosensitive composition and the photosensitive composition for measurement are, for example, EUV exposure resist compositions, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have fluorine and iodine atoms as substituents.

[0073] In terms of further improving acid decomposition properties, when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group that protects a polar group, it is also preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0074] Other leaving groups that are removed by the action of an acid may 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.

[0075] As the repeating unit (Aa), the repeating unit represented by formula (A) is also preferred.

[0076] [ka]

[0077] 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. In addition, one preferred embodiment of the repeating unit represented by formula (A) is one in which at least one of L1, R1, and R2 is a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups 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 (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, L1 is preferably -CO-, an arylene group, or an arylene group-which may have a fluorine atom or an iodine atom-, and more preferably -CO-, an arylene group, or an arylene group-which may have a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. When the alkylene group has a fluorine atom or an iodine atom, the total number of fluorine atoms and iodine atoms contained in the alkylene group is not particularly limited, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0078] 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. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0079] R2 represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. Examples of leaving groups that may have a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that have a fluorine atom or an iodine atom, and the preferred embodiment is the same.

[0080] As the repeating unit (Aa), the repeating unit represented by the general formula (AI) is also preferred.

[0081] [ka]

[0082] In the general formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have substituents. T represents a single bond or a divalent linking group. Each of Rx1 to Rx3 independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an alkenyl group. However, if 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. Two of Rx1 to Rx3 may bond together to form a cycloalkyl group (monocyclic or polycyclic).

[0083] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0084] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, 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, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0085] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. In addition, polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. Examples of alkenyl groups in Rx1 to Rx3 include vinyl groups. Examples of aryl groups Rx1 to Rx3 include phenyl groups. The repeating unit represented by the general formula (AI) is preferably configured such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded together to form the cycloalkyl group described above.

[0086] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0087] The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth)acrylate 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).

[0088] The resin (A) may have one repeating unit (Aa) alone, or it may have two or more repeating units. The content of repeating units (Aa) (total content if two or more types of repeating units (Aa) are present) is preferably 15 to 80 mol%, and more preferably 20 to 70 mol%, relative to the total number of repeating units in the resin (A).

[0089] The resin (A) preferably has at least one repeating unit (Aa) selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII).

[0090] [ka]

[0091] In the general formula (A-VIII), R5 represents a tert-butyl group or a -CO-O-(tert-butyl) group. In general formula (A-IX), R6 and R7 each independently represent a monovalent organic group. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. In the general formula (AX), p represents either 1 or 2. In the general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms. In general formula (A-XII), R 10 This represents an alkyl group or adamantyl group having 1 to 3 carbon atoms.

[0092] ≪Repeating unit with acid group (A-1)≫ The resin (A) may have repeating units (A-1) having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 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. If the acid group content is within the above range, development proceeds smoothly, resulting in superior pattern shape and resolution. Preferred acid groups include, for example, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF3)(OH)-CF2- formed in this way is also preferred as an acid group. Alternatively, 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 (A-1) is preferably a repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and is different from the repeating unit having a lactone group, sultone group, or carbonate group (A-2) described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0093] As for the repeating unit having an acidic group, a repeating unit having a phenolic hydroxyl group is preferred, and a repeating unit represented by formula (Y) is more preferred.

[0094] [ka]

[0095] In formula (Y), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. L represents a single bond or a divalent linking group having an oxygen atom. A single bond is preferred for L. R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or aryloxycarbonyl group. If there are multiple Rs, they may be the same or different. If there are multiple Rs, they may be bonded to each other to form a ring. A hydrogen atom is preferred as R. 'a' represents an integer between 1 and 3. b represents an integer between 0 and (5-a).

[0096] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] As a repeating unit having an acid group, for example, a repeating unit having a phenolic hydroxyl group described in paragraphs 0089 to 0100 of Japanese Patent Application Publication No. 2018-189758 can also be suitably used.

[0101] When resin (A) contains repeating units (A-1) having acidic groups, the reference photosensitive composition and the measurement photosensitive composition containing resin (A) are preferred for KrF exposure, EB exposure, or EUV exposure. In this embodiment, the content of repeating units having acidic groups in resin (A) is preferably 30 to 90 mol%, and more preferably 35 to 60 mol%, relative to the total repeating units in resin (A).

[0102] ≪A repeating unit (A-2) having at least one selected from the group consisting of lactone structure, sultone structure, carbonate structure, and hydroxyadamantane structure≫ The resin (A) may have repeating units (A-2) having at least one selected from the group consisting of lactone structures, carbonate structures, sultone structures, and hydroxyadamantane structures.

[0103] The lactone structure or sultone structure in the repeating unit having a lactone structure or sultone structure is not particularly limited, but a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure is preferred, and a 5-7 membered ring lactone structure is more preferably one in which other ring structures are fused to form a bicyclo or spiro structure, or a 5-7 membered ring sultone structure is more preferably one in which other ring structures are fused to form a bicyclo or spiro structure. Examples of repeating units having a lactone or sultone structure include the repeating units described in paragraphs 0094-0107 of International Publication No. 2016 / 136354.

[0104] The resin (A) may have repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure. Examples of repeating units having a carbonate structure include the repeating units described in paragraphs 0106-0108 of International Publication No. 2019 / 054311.

[0105] The resin (A) may have repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include the repeating unit represented by the following general formula (AIIa).

[0106] [ka]

[0107] In general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R2c to R4c represents a hydroxyl group. Preferably, one or two of R2c to R4c are hydroxyl groups and the rest are hydrogen atoms.

[0108] ≪Repeating units containing fluorine or iodine atoms≫ The resin (A) may have repeating units having fluorine atoms or iodine atoms. Examples of repeating units having fluorine atoms or iodine atoms include the repeating units described in paragraphs 0080 to 0081 of Japanese Patent Application Publication No. 2019-045864.

[0109] ≪Repeating units with photoacid-generating groups≫ The resin (A) may also have repeating units other than those described above, which have groups that generate acid upon irradiation with radiation. Examples of repeating units having a photoacid generating group include the repeating units described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2019-045864.

[0110] <<Repeating units with alkali-soluble groups>> The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohols substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol group), with carboxyl groups being preferred. The presence of repeating units with alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include repeating units in which alkali-soluble groups are directly bonded to the main chain of the resin, such as repeating units made of acrylic acid and methacrylic acid, or repeating units in which alkali-soluble groups are bonded to the main chain of the resin via a linking group. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. As repeating units having alkali-soluble groups, repeating units made of acrylic acid or methacrylic acid are preferred.

[0111] ≪Repeating units that do not possess either an acid-degradable group or a polar group≫ The resin (A) may further have repeating units that do not have either an acid-degradable group or a polar group. The repeating units that do not have either an acid-degradable group or a polar group preferably have an alicyclic hydrocarbon structure.

[0112] Examples of repeating units that do not have either an acid-degradable group or a polar group include the repeating units described in paragraphs 0236-0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0113] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer droplet properties, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0114] ≪Properties of Resin (A)≫ Resin (A) may consist entirely of repeating units derived from (meth)acrylate monomers. In this case, any resin can be used in which all repeating units are derived from methacrylate monomers, all repeating units are derived from acrylate monomers, or all repeating units are derived from both methacrylate monomers and acrylate monomers. It is preferable that the repeating units derived from acrylate monomers constitute 50 mol% or less of the total repeating units in resin (A).

[0115] When the reference photosensitive composition and the measurement photosensitive composition are for argon fluoride (ArF) exposure, it is preferable that the resin (A) substantially does not contain aromatic groups from the viewpoint of ArF light transmittance. More specifically, it is preferable that the repeating units having aromatic groups are 5 mol% or less of the total repeating units of the resin (A), more preferably 3 mol% or less, and ideally even more preferably 0 mol%, i.e., that there are no repeating units having aromatic groups. Furthermore, when the reference photosensitive composition and the measurement photosensitive composition are for ArF exposure, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure, and preferably does not contain either fluorine or silicon atoms.

[0116] When the reference photosensitive composition and the measurement photosensitive composition are for krypton fluoride (KrF) exposure, EB exposure, or EUV exposure, the resin (A) preferably has repeating units having aromatic hydrocarbon groups, and more preferably has repeating units having phenolic hydroxyl groups. Examples of repeating units having phenolic hydroxyl groups include the repeating units exemplified above as the repeating units having acidic groups (A-1), and repeating units derived from hydroxystyrene (meth)acrylate. Furthermore, when the reference photosensitive composition and the measurement photosensitive composition are for KrF exposure, EB exposure, or EUV exposure, it is also preferable that the resin (A) has repeating units having a structure in which the hydrogen atoms of the phenolic hydroxyl group are protected by a leaving group (a group that decomposes and leaves due to the action of an acid). When the reference photosensitive composition and the measurement photosensitive composition are for KrF exposure, EB exposure, or EUV exposure, the content of repeating units having aromatic hydrocarbon groups in resin (A) is preferably 30 to 100 mol%, and more preferably 35 to 100 mol%, relative to the total repeating units in resin (A).

[0117] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). The weight-average molecular weight (Mw) of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight-average molecular weight (Mw) of resin (A) to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, as well as deterioration of developability and deterioration of film-forming ability due to increased viscosity can be prevented. The weight-average molecular weight (Mw) of resin (A) is the polystyrene equivalent value measured by the GPC method described above. The degree of dispersion (molecular weight distribution) of resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the pattern and the better the roughness.

[0118] In the reference photosensitive composition and the photosensitive composition for measurement, the content of resin (A) is preferably 50 to 99.9% by mass, and more preferably 60 to 99.0% by mass, relative to the total solid content of the reference photosensitive composition and the photosensitive composition for measurement. Furthermore, resin (A) may be used alone or in combination of two or more types.

[0119] <Photoacid Generator> The reference photosensitive composition and the photosensitive composition for measurement contain a photoacid generator (B). The photoacid generator (B) is not particularly limited as long as it is a compound that generates acid upon irradiation with radiation. The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Alternatively, both the low molecular weight compound form and the polymer-integrated form may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, its weight-average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). The photoacid generator (B) is preferably in the form of a low molecular weight compound. The photoacid generator (B) is not particularly limited as long as it is a known compound, but a compound that generates an organic acid upon irradiation with radiation is preferred, and a photoacid generator having a fluorine atom or an iodine atom in its molecule is more preferred. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0120] The volume of acid generated by the photoacid generator (B) is not particularly limited, but to suppress the diffusion of the acid generated during exposure into the unexposed areas and improve resolution, 240 Å is preferred. 3 The above is preferable, 305Å 3 The above is more preferable, 350 Å 3 The above is even more preferable, 400Å 3 The above is particularly preferable. Furthermore, from the viewpoint of sensitivity or solubility in the coating solvent, the volume of acid generated from the photoacid generator (B) is 1500 Å. 3 The following is preferable, 1000 Å 3 The following is more preferable: 700 Å 3The following is even more preferable. The above volume values ​​are determined using "WinMOPAC" manufactured by Fujitsu Limited. To calculate the above volume values, first, the chemical structure of the acid in each example is input, then, using this structure as the initial structure, the most stable conformation of each acid is determined by molecular force field calculation using the MM (Molecular Mechanics) 3 method, and then, by performing molecular orbital calculations using the PM (Parameterized Model number) 3 method for these most stable conformations, the "accessible volume" of each acid can be calculated.

[0121] The structure of the acid generated by the photoacid generator (B) is not particularly limited, but a strong interaction between the acid generated by the photoacid generator (B) and the resin (A) is preferable in order to suppress acid diffusion and improve resolution. From this point of view, if the acid generated by the photoacid generator (B) is an organic acid, it is preferable that it has a polar group in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonylsulfonylimide acid groups, bissulfonylimide acid groups, and trissulfonylmethidic acid groups. Examples of polar groups include ether groups, ester groups, amide groups, acyl groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, carbamate groups, hydroxyl groups, and mercapto groups. The number of polar groups in the generated acid is not particularly limited, but it is preferably one or more, and more preferably two or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than six, and more preferably less than four.

[0122] In particular, the photoacid generator (B) is preferably a photoacid generator consisting of an anion portion and a cation portion. Examples of the photoacid generator (B) include the photoacid generator described in paragraphs 0144 to 0173 of Japanese Patent Application Publication No. 2019-045864.

[0123] The content of the photoacid generator (B) is not particularly limited, but is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 35% by mass, relative to the total solid content of the reference photosensitive composition and the measurement photosensitive composition. The photoacid generator (B) may be used alone or in combination of two or more types. When using two or more photoacid generators (B) in combination, it is preferable that their total amount is within the above range.

[0124] <Acid diffusion control agent (C)> The reference photosensitive composition and the photosensitive composition for measurement may contain an acid diffusion control agent (C). The acid diffusion control agent (C) traps the acid generated from the photoacid generator (B) during exposure and acts as a quencher to suppress the reaction of the acid-degradable resin in the unexposed area due to excess generated acid. Examples of acid diffusion control agents (C) that can be used include basic compounds (CA), basic compounds whose basicity decreases or disappears upon irradiation with radiation (CB), onium salts (CC) that are relatively weak acids to the photoacid generator (B), low molecular weight compounds (CD) that have a nitrogen atom and a group that is eliminated by the action of acid, and onium salt compounds (CE) that have a nitrogen atom in the cation portion. In the reference photosensitive composition and the photosensitive composition for measurement, known acid diffusion control agents can be used as appropriate. For example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458 can be suitably used as acid diffusion control agents (C).

[0125] Examples of basic compounds (CA) include the repeating units described in paragraphs 0188 to 0208 of Japanese Patent Publication No. 2019-045864.

[0126] In the reference photosensitive composition and the photosensitive composition for measurement, an onium salt (CC), which is a relatively weak acid with respect to the photoacid generator (B), can be used as the acid diffusion control agent (C). When a photoacid generator (B) and an onium salt that generates an acid that is relatively weaker than the acid produced by the photoacid generator (B) are mixed and used, when the acid produced by the photoacid generator (B) collides with the onium salt containing an unreacted weak acid anion due to irradiation with active light or radiation, salt exchange occurs, releasing the weak acid and producing an onium salt containing a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so the acid is seemingly deactivated and acid diffusion can be controlled.

[0127] Examples of onium salts that are relatively weak acids with respect to the photoacid generator (B) include the onium salts described in paragraphs 0226 to 0233 of Japanese Patent Application Publication No. 2019-070676.

[0128] When the reference photosensitive composition and the photosensitive composition for measurement contain an acid diffusion control agent (C), the content of the acid diffusion control agent (C) (total if there are multiple types) is preferably 0.1 to 10.0% by mass, and more preferably 0.1 to 5.0% by mass, relative to the total solid content of the reference photosensitive composition and the photosensitive composition for measurement. The acid diffusion control agent (C) may be used alone or in combination of two or more types. When using two or more acid diffusion control agents (C) in combination, it is preferable that their total amount is within the above range.

[0129] <Hydrophobic resin (E)> The reference photosensitive composition and the photosensitive composition for measurement may contain a hydrophobic resin (E) that is different from the resin (A) mentioned above. The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding a hydrophobic resin (E) include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0130] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin (E) preferably contains one or more of the following: "fluorine atoms," "silicon atoms," and "CH3 substructures contained in the side chain portion of the resin," and more preferably two or more. Furthermore, the hydrophobic resin (E) preferably contains hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains.

[0131] If the hydrophobic resin (E) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chains.

[0132] When the hydrophobic resin (E) contains a fluorine atom, the fluorine atom-containing substructure is preferably an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom. A fluorine-containing alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than fluorine atoms. A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than a fluorine atom. Examples of aryl groups having a fluorine atom include phenyl groups and naphthyl groups, in which at least one hydrogen atom of an aryl group is substituted with a fluorine atom, and they may also have substituents other than fluorine atoms. Examples of repeating units having fluorine or silicon atoms are illustrated in paragraph 0519 of U.S. Patent Application Publication No. 2012 / 0251948.

[0133] Furthermore, as described above, it is also preferable that the hydrophobic resin (E) has a CH3 substructure in its side chain portion. Here, the CH3 substructures in the side chain portion of the hydrophobic resin include CH3 substructures having ethyl groups and propyl groups, etc. On the other hand, methyl groups directly bonded to the main chain of the hydrophobic resin (E) (for example, α-methyl groups of repeating units having a methacrylic acid structure) are not included in the CH3 substructure in this invention because their contribution to the surface segregation of the hydrophobic resin (E) is small due to the influence of the main chain.

[0134] With regard to hydrophobic resin (E), refer to paragraphs

[0348] to

[0415] of Japanese Patent Publication No. 2014-010245, and these contents are incorporated herein by reference. As the hydrophobic resin (E), resins described in Japanese Patent Publication No. 2011-248019, Japanese Patent Publication No. 2010-175859, and Japanese Patent Publication No. 2012-032544 can also be preferably used.

[0135] When the reference photosensitive composition and the measurement photosensitive composition contain a hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20% by mass, and more preferably 0.1 to 15% by mass, relative to the total solid content of the reference photosensitive composition and the measurement photosensitive composition.

[0136] <Solvent (F)> The reference photosensitive composition and the photosensitive composition for measurement may contain a solvent (F). When the reference photosensitive composition and the measurement photosensitive composition are radiation-sensitive resin compositions for EUV exposure, the solvent (F) preferably contains (F1) propylene glycol monoalkyl ether carboxylate and (F2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. In this case, the solvent may further contain components other than components (F1) and (F2). A solvent containing at least one of components (F1) and (F2) is preferable when used in combination with the resin (A) described above, because it improves the coatability of the reference photosensitive composition and the photosensitive composition for measurement, and enables the formation of patterns with fewer development defects.

[0137] Furthermore, when the reference photosensitive composition and the photosensitive composition for measurement are radiation-sensitive resin compositions for ArF, examples of solvents (F) include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0138] The solvent (F) content in the reference photosensitive composition and the photosensitive composition for measurement is preferably determined so that the solid content concentration is 0.5 to 40% by mass. In one embodiment of the reference photosensitive composition and the photosensitive composition for measurement, it is also preferable that the solid content concentration is 10% by mass or more.

[0139] <Surfactant (H)> The reference photosensitive composition and the measurement photosensitive composition may contain a surfactant (H). The inclusion of a surfactant (H) allows for superior adhesion and the formation of patterns with fewer development defects. As the surfactant (H), fluorine-based and / or silicone-based surfactants are preferred. Examples of fluorine-based and / or silicone-based surfactants include the surfactant described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, in addition to the known surfactants described above, surfactant (H) may be synthesized using a fluoroaliphatic compound produced by telomerization (also known as the telomer method) or oligomerization (also known as the oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as surfactant (H). This fluoroaliphatic compound can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2002-90991.

[0140] These surfactants (H) may be used individually or in combination of two or more. The surfactant (H) content is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, relative to the total solid content of the reference photosensitive composition and the photosensitive composition for measurement.

[0141] <Other additives> The reference photosensitive composition and the photosensitive composition for measurement may further contain a crosslinking agent, an alkali-soluble resin, a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in the developer. [Examples]

[0142] The features of the present invention will be further described in detail below with reference to examples. The materials, reagents, amounts and proportions of substances, and procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.

[0143] [Preparation of composition] Each composition was prepared by mixing the components listed in Table 1 below. The "Content (mass%)" column in Table 1 represents the content of each component relative to the total solid content in the composition. The solid content concentration of all compositions was 1.5% by mass. R in Table 1 represents the dissolution index (R) of the monomer having an acid-decomposable group that constitutes the repeating unit contained in the acid-decomposable resin, and the difference in dissolution index (ΔR) before and after acid elimination. Note that R B and ΔR B each represent the dissolution index (R) of the monomer represented by the following formula B and the difference in dissolution index (ΔR) before and after acid elimination. Also, R C and ΔR C each represent the dissolution index (R) of the monomer represented by the following formula C and the difference in dissolution index (ΔR) before and after acid elimination.

[0144]

Table 1

[0145] The acid-decomposable resins A-1 and A-2 are resins obtained by radical polymerization of monomers represented by the following formula, and are resins having repeating units derived from each monomer. The content, molecular weight, and dispersity of each repeating unit are shown in Table 2.

[0146]

Chemical formula

[0147]

Table 2

[0148] B-1: Photoacid generator shown below

Chemical formula

[0149] C-1: Acid diffusion controller shown below

Chemical formula

[0150] F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: γ-Butyrolactone F-4: 2-Heptanone

[0151] [Preparation of treatment liquid] The treatment liquids for the examples and comparative examples were prepared by mixing so as to have the components and contents shown in the following table. The content of metal X was adjusted by passing the treatment liquid prepared for the filter until it reached a predetermined content or by adding metal X. Also, the water content in each treatment liquid was adjusted to be 20 to 1000 mass ppm with respect to the total mass of each treatment liquid. The contents of various components were calculated from the charged amounts or measured using the measurement methods for the contents of various components described above. In each treatment liquid, the content of the organic solvent corresponds to the remainder other than the components and water described in the table below.

[0152] [Aliphatic hydrocarbon] ·Undecane

[0153] [Ester solvent] ·Butyl acetate

[0154] [Aromatic hydrocarbon] ·C1: 1-ethyl-3,5-dimethyl-benzene (C 10 H 14 ) ·C2: 1,2,3,5-tetramethyl-benzene (C 10 H 14 ) ·C3: (1-methylbutyl)-benzene (C 11 H 16 ) ·C4: 1,2,3,4-tetrahydro-naphthalene (C 10 H 12 )

[0155] In Table 3 below, each description indicates the following. The "Content (a)" column for "Organic Solvent" indicates the mass of aliphatic hydrocarbons when the total mass of the organic solvent is set to 100. The "Content (b)" column for "Organic Solvents" indicates the content of ester-based solvents when the total mass of organic solvents is set to 100. Therefore, for example, in treatment solution 1, the mass ratio of aliphatic hydrocarbons to ester solvents is 10:90. The "total" column for "aromatic hydrocarbons" indicates the total content of aromatic hydrocarbons C1-C4 relative to the total mass of the treated liquid. The "C1" to "C4" columns under "Aromatic Hydrocarbons" indicate the respective content (mass ppm) of aromatic hydrocarbons C1 to C4 relative to the total mass of the treated solution. The "total" column for "Metal X" shows the total content (mass ppt) of Fe, Ni, and Al relative to the total mass of the treatment solution. The columns for "Fe," "Ni," and "Al" under "Metal X" indicate the respective content (mass ppt) of Fe, Ni, and Al relative to the total mass of the treatment solution. The column "(c) / (e)" shows the mass ratio of the aromatic hydrocarbon content (total content of aromatic hydrocarbons C1-C4 above) to the metal X content (total content of Fe, Ni, and Al) (aromatic hydrocarbon content / metal X content (total content of Fe, Ni, and Al)). Also, "E+n" is "×10 n This indicates "En" is "×10 -n This indicates that n is a non-negative integer. Specifically, "1.2E+06" is "1.2 × 10 6 This indicates "". Note that "E+n" and "En" above have the same meaning in other columns as well.

[0156] [Table 3]

[0157] [Example 1] <Test 1> (Exam 1-1) On a 12-inch silicon wafer, a composition AL-412 (manufactured by Brewer Science) for forming a lower layer film was applied and baked at 205 °C for 60 seconds to form a lower layer film with a thickness of 20 nm. Then, Composition 1 prepared above was applied and baked at 90 °C for 60 seconds (PB) to form a resist film with a thickness of 35 nm. Thus, a silicon wafer having a resist film was fabricated. The above operation was repeated twice to fabricate two silicon wafers having resist films. The resist film on the silicon wafer having one obtained resist film was brought into contact with Processing Liquid 1 to remove the resist film, and the number of defects on the silicon wafer from which the resist film was removed was measured using UVision5 (manufactured by AMAT). The number of defects was 100 pieces / wafer. Pattern irradiation was performed on the other silicon wafer having a resist film using an EUV exposure apparatus (manufactured by ASML, NXE-3400, NA0.33, Quadrupole, outer sigma 0.68, inner sigma 0.36). As a reticle, a photomask with a line size = 20 nm and a line:space = 1:1 was used. Then, after baking (PEB) at 100 °C for 60 seconds, it was paddled with Processing Liquid 1 for 30 seconds for development, and the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to obtain a line and space pattern with a pitch of 40 nm. When LWR was measured from the obtained pattern, it was 3.0 nm.

[0158] (Test 1-2) Next, using Resist Composition 1, the same operation as above was repeated once more. Specifically, on a 12-inch silicon wafer, a composition AL-412 (manufactured by Brewer Science) for forming a lower layer film was applied and baked at 205 °C for 60 seconds to form a lower layer film with a thickness of 20 nm. Then, Composition 1 prepared above was applied and baked at 90 °C for 60 seconds (PB) to form a resist film with a thickness of 35 nm. Thus, a silicon wafer having a resist film was fabricated. The above operation was repeated twice to fabricate two silicon wafers having resist films. The resist film on a silicon wafer containing one of the obtained resist films was brought into contact with processing solution 1 to remove the resist film, and the number of defects on the silicon wafer from which the resist film had been removed was measured using UVision5 (manufactured by AMAT). The number of defects was 105 per wafer. A silicon wafer with another resist film was patterned using an EUV exposure system (ASML EUV scanner NXE3300 (NA 0.33), Quadrupole, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the reticle. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddleding in processing solution 1 for 30 seconds, and then the wafer was rotated at a speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 40 nm. The LWR was measured from the obtained pattern and found to be 3.1 nm.

[0159] In the results described above, the number of defects after removing the resist film formed using composition 1 with processing solution 1 was measured twice. The number of defects in the first measurement was 100 per wafer, and the number of defects in the second measurement was 105 per wafer. The results were almost the same, and the ratio of the number of defects (number of defects in the second measurement / number of defects in the first measurement) was 1.05. Furthermore, the LWR result after the first pattern formation was 3.0 nm, and the LWR result after the second pattern formation was 3.1 nm. The results were almost the same, and the difference in LWR was 0.1 nm.

[0160] <Exam 2> The evaluation was carried out using the same procedure as in <Test 1> (Test 1-2) above, except that composition 2 was used instead of composition 1. The number of defects after removing the resist film formed using composition 1 with processing solution 1 was 100 per wafer, and the number of defects after removing the resist film formed using composition 2 with processing solution 1 was 120 per wafer. The ratio of the number of defects (number of defects in the second step / number of defects in the first step) was 1.20, which was larger than in the case of <Test 1> described above. Furthermore, the LWR result when the first pattern formation was performed using composition 1 was 3.0 nm, and the LWR result when the second pattern formation was performed using composition 2 was 3.6 nm. The difference in LWR was 0.6 nm, which was larger than in the case of <Test 1> described above.

[0161] The results of the above-mentioned <Test 1> and <Test 2> confirmed that when the ratio of the number of defects was small, the difference in LWR was also small, and when the ratio of the number of defects was large, the difference in LWR was also large. This result demonstrates that the number of defects is closely related to the evaluation result of LWR. Based on the above results, for example, if a defect ratio of 0.9 to 1.1 is set as the acceptable range, and a different photosensitive composition is tested instead of composition 1 used in (Test 1-2) of <Test 1> above, if the defect ratio is within the above acceptable range, it can be determined that the LWR result also indicates an LWR result identified as that of resist composition 1.

[0162] [Example 2] The experiment was conducted using the same procedure as in Example 1, except that treatment solution 2 was used instead of treatment solution 1. The results are shown in Table 4, and, as in Example 1, it was demonstrated that the number of defects was closely related to the evaluation result of LWR. [Example 3] The experiment was conducted using the same procedure as in Example 1, except that treatment solution 5 was used instead of treatment solution 1. The results are shown in Table 4, and, as in Example 1, it was demonstrated that the number of defects was closely related to the evaluation result of LWR. [Example 4] The experiment was conducted using the same procedure as in Example 1, except that treatment solution 6 was used instead of treatment solution 1. The results are shown in Table 4, and, as in Example 1, it was demonstrated that the number of defects was closely related to the evaluation result of LWR.

[0163] [Comparative Example 1] When the same procedure as in <Test 2> of [Example 1] was performed using processing solution 3 instead of processing solution 1, as shown in Table 4, the number of defects after removing the resist film formed with composition 2 with processing solution 3 was 105 per wafer, and the LWR result when the second pattern formation was performed using composition 2 was 4.0 nm. As shown in Table 4, in this Comparative Example 1, despite the ratio of the number of defects (number of defects in the second attempt / number of defects in the first attempt) being close at 1.05, the difference between the LWR when the first pattern formation was performed using composition 1 and the LWR when the second pattern formation was performed using composition 2 was large at 1.0 nm, indicating no correlation between the number of defects and the difference in LWR. These results confirm that the photosensitive composition cannot be tested if the specified processing solution is not used.

[0164] [Comparative Example 2] When the same procedure as in <Test 2> of [Example 1] was performed using processing solution 4 instead of processing solution 1, as shown in Table 4, the number of defects after removing the resist film formed with composition 2 with processing solution 3 was 97 per wafer, and the LWR result when the second pattern formation was performed using composition 2 was 4.2 nm. As shown in Table 4, in this Comparative Example 2, despite the ratio of the number of defects (number of defects in the second attempt / number of defects in the first attempt) being close at 0.97, the difference between the LWR when the first pattern formation was performed using composition 1 and the LWR when the second pattern formation was performed using composition 2 was large at 1.2 nm, indicating no correlation between the number of defects and the difference in LWR. These results confirm that the photosensitive composition cannot be tested if the specified processing solution is not used.

[0165] In Table 4, the "Correlation" column indicates whether there is a correlation between the number of defects and the LWR (lower weight ratio), with "Yes" indicating a correlation and "No" indicating no correlation.

[0166] [Table 4]

[0167] As shown in Table 4 above, it was confirmed that the desired effect can be obtained with the testing method of the present invention.

[0168] Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that the mass ratio of undecane to butyl acetate was 5:95, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that the mass ratio of undecane to butyl acetate was 15:85, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that the mass ratio of undecane to butyl acetate was 40:60, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that the mass ratio of undecane to butyl acetate was 60:40, it was confirmed that the number of defects was closely related to the evaluation result of LWR, similar to Example 1.

[0169] Furthermore, in Example 1, when a processing solution with the same composition as processing solution 1 was used, except that undecane was replaced with decane, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a processing solution with the same composition as processing solution 1 was used, except that undecane was replaced with dodecane, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that butyl acetate was replaced with isoamyl acetate, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 1, when a treatment solution with the same composition as treatment solution 1 was used, except that butyl acetate was replaced with isoamyl formate, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 1. Furthermore, in Example 2, when a processing solution with the same composition as processing solution 2 was used, except that undecane was replaced with decane, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 2. Furthermore, in Comparative Example 1, when a processing solution with the same composition as processing solution 3 was used, except that undecane was replaced with decane, it was confirmed that, similar to Comparative Example 1, the number of defects was not correlated with the LWR evaluation results. Furthermore, in Comparative Example 2, when a processing solution with the same composition as processing solution 4 was used, except that undecane was replaced with decane, it was confirmed that, similar to Comparative Example 2, the number of defects was not correlated with the evaluation results of LWR. Furthermore, in Example 2, when a processing solution with the same composition as processing solution 2 was used, except that undecane was replaced with dodecane, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 2. Furthermore, in Comparative Example 1, when a treatment solution with the same composition as treatment solution 3 was used, except that undecane was replaced with dodecane, it was confirmed that, similar to Comparative Example 1, the number of defects was not correlated with the evaluation results of LWR. Furthermore, in Comparative Example 2, when a processing solution with the same composition as processing solution 4 was used, except that undecane was replaced with dodecane, it was confirmed that, similar to Comparative Example 2, the number of defects was not correlated with the evaluation results of LWR. Furthermore, in Example 2, when a treatment solution with the same composition as treatment solution 2 was used, except that butyl acetate was replaced with amyl acetate, it was confirmed that the number of defects was closely related to the LWR evaluation results, similar to Example 2. Furthermore, in Comparative Example 1, when a treatment solution with the same composition as treatment solution 3 was used, except that butyl acetate was replaced with amyl acetate, it was confirmed that, similar to Comparative Example 1, the number of defects was not correlated with the evaluation results of LWR. In Comparative Example 2, it was also confirmed that when a treatment liquid having the same composition as Treatment Liquid 4 was used except that butyl acetate was changed to amyl acetate, the number of defects had no correlation with the LWR evaluation result, as in Comparative Example 2. In Example 2, it was also confirmed that when a treatment liquid having the same composition as Treatment Liquid 2 was used except that butyl acetate was changed to isoamyl formate, the number of defects was closely related to the LWR evaluation result, as in Example 2. In Comparative Example 1, it was also confirmed that when a treatment liquid having the same composition as Treatment Liquid 3 was used except that butyl acetate was changed to isoamyl formate, the number of defects had no correlation with the LWR evaluation result, as in Comparative Example 1. In Comparative Example 2, it was also confirmed that when a treatment liquid having the same composition as Treatment Liquid 4 was used except that butyl acetate was changed to isoamyl formate, the number of defects had no correlation with the LWR evaluation result, as in Comparative Example 2.

[0170] In Example 1, when a treatment liquid having the same composition as Treatment Liquid 1 was used except that the mass ratio of the content of aromatic hydrocarbon to the content of Metal X was 5.0×10 7 it was also confirmed that the number of defects was closely related to the LWR evaluation result, as in Example 1.

[0171] In Example 1, when a composition having the same composition as Composition 1 was used except that acid-decomposable resin A-1 was replaced with acid-decomposable resin A-3 (see below), it was also confirmed that the number of defects was closely related to the LWR evaluation result, as in Example 1. Table 5 below shows the content of each repeating unit of acid-decomposable resin A-3, molecular weight, dispersity, and the dissolution index (R) and dissolution index difference (ΔR) of the monomer having an acid-decomposable group, respectively.

[0172] <​​​​​​​​​​​

[0174] In Example 1, even when a composition with the same composition as Composition 1 was used, except that acid-degradable resin A-1 and acid-degradable resin A-3 were used in a mass ratio of 7:3 instead of acid-degradable resin A-1, it was confirmed that the number of defects was closely related to the LWR evaluation result, similar to Example 1.

[0175] In Example 1, even when a composition with the same composition as Composition 1 was used, except that photoacid generator B-2 (see below) was used instead of photoacid generator B-1, it was confirmed that the number of defects was closely related to the LWR evaluation result, just as in Example 1.

[0176] [ka]

[0177] In Example 1, even when a composition with the same composition as Composition 1 was used, except that photoacid generator B-1 and photoacid generator B-2 were used in a mass ratio of 1:1 instead of photoacid generator B-1, it was confirmed that the number of defects was closely related to the LWR evaluation result, similar to Example 1. [Explanation of symbols]

[0178] S10, S12, S14, S16, S20, S21, S22, S24 Step S30, S31, S32, S34, S40, S22, S24 Step S40, S42, S44 Step

Claims

1. A resist film is formed on a substrate 1 using a standard photosensitive composition containing an acid-degradable resin having a group that decomposes to produce a polar group by the action of an acid, and a photoacid generator, and the resist film on the substrate 1 is removed using a processing solution. Step 1 involves measuring the number of defects on the substrate 1 from which the resist film has been removed, and obtaining reference data. Step 2 involves forming a resist film on a substrate 2 using a measurement photosensitive composition containing the same type of components as those contained in the aforementioned reference photosensitive composition, removing the resist film on the substrate 2 using a processing solution, and measuring the number of defects on the substrate 2 from which the resist film has been removed to obtain measurement data. The process includes a step 3 in which the reference data and the measurement data are compared to determine whether they are within an acceptable range. The aforementioned processing liquid contains an aromatic hydrocarbon, an organic solvent, and metal X. The organic solvent does not contain the aromatic hydrocarbon and contains an aliphatic hydrocarbon having 10 or more carbon atoms and an ester solvent having 2 to 10 carbon atoms. The content of the aromatic hydrocarbon is 1% by mass or less relative to the total mass of the treatment liquid. The aliphatic hydrocarbon content is 3 to 30% by mass relative to the total mass of the treatment solution. The content of the ester-based solvent is 60 to 95% by mass of the total mass of the treatment solution. The metal X is at least one metal selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal X content is 5.0 × 10 ４ ~2.0 x 10 １０ A method for testing photosensitive compositions.

2. The method for testing a photosensitive composition according to claim 1, wherein in step 3, if the measurement data falls outside the acceptable range, the components of the photosensitive composition for measurement are adjusted.

3. A method for testing a photosensitive composition according to claim 1 or 2, wherein in step 1 and step 2, the resist film on the substrate 1 and the resist film on the substrate 2 are, respectively, resist films that have been exposed by pattern exposure after the resist film has been formed.

4. The method for testing a photosensitive composition according to claim 3, wherein the pattern exposure in step 1 and step 2 uses any of the following: KrF excimer laser light, ArF excimer laser light, electron beam, and extreme ultraviolet light.

5. The method for testing a photosensitive composition according to claim 1 or 2, wherein the number of defects on the substrate 1 from which the resist film on the substrate 1 has been removed and the number of defects on the substrate 2 from which the resist film on the substrate 2 has been removed are measured using a defect inspection device, respectively.

6. The method for testing a photosensitive composition according to claim 1 or 2, wherein the acid-degradable resin comprises repeating units having phenolic hydroxyl groups.

7. The aliphatic hydrocarbon is undecane, The method for testing a photosensitive composition according to claim 1 or 2, wherein the ester solvent is butyl acetate.

8. A method for testing a photosensitive composition according to claim 7, wherein the ratio of the content of butyl acetate to the content of undecane is 65 / 35 to 99 / 1.

9. The method for testing a photosensitive composition according to claim 8, wherein the ratio of the content of butyl acetate to the content of undecane is 90 / 10.

10. The acid-degradable resin has repeating units derived from monomers that decompose upon the action of acid to produce polar groups. All of the monomers are represented by formula (1) and have a solubility index (R) of 2.0 to 5.0 (MPa) based on the Hansen solubility parameter in the processing solution. １／２ And, At least one of the monomers has a difference in solubility index (ΔR) before and after acid elimination of 4.0 (MPa). １／２ The above is the method for testing a photosensitive composition according to claim 1 or 2. formula (1) R=(4(δm1-δm2) ２ + (dp1-dp2) ２ + (δη1-δη2) ２ ) １／２ δd1 represents the dispersion term in the Hansen solubility parameter of the monomer. δp1 represents the polarity term in the Hansen solubility parameter of the monomer. δh1 represents the hydrogen bonding term in the Hansen solubility parameter of the monomer. δd2 represents the dispersion term in the Hansen solubility parameter of the treatment solution. δp2 represents the polarity term in the Hansen solubility parameter of the processing solution. δh2 represents the hydrogen bonding term in the Hansen solubility parameter of the treatment solution.

11. In the reference data, the number of defects on the base material 1 is 0.0001 to 10 / cm ２ The method for assaying a photosensitive composition according to claim 1 or 2, wherein the number is as defined above.

12. A method for producing a photosensitive composition, comprising a method for testing the photosensitive composition according to claim 1 or 2.

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