Method for testing photosensitive compositions, method for producing photosensitive compositions

Abstract

The present invention provides: a method for verifying a photosensitive composition, the method being capable of easily verifying whether or not the photosensitive composition has a specific LWR; and a method for producing a photosensitive composition. This method for verifying a photosensitive composition comprises: a step 1 in which a resist film is formed on a base material with use of a reference photosensitive composition that contains a photoacid generator and an acid-decomposable resin having a group that is decomposed by the action of an acid and generates a polar group, a resist pattern is subsequently formed by exposing the resist film to light and developing the light-exposed resist film with use of a developer solution, and one reference datum that is selected from the group consisting of the line width or the space width of a linear resist pattern, the opening diameter of an opening in a resist pattern, and the dot diameter of a dot-like resist pattern is acquired; a step 2 in which a resist film is formed on a base material with use of a photosensitive composition for measurement containing components that are the same as the components contained in the reference photosensitive composition, a resist pattern is subsequently formed by exposing the resist film to light and developing the light-exposed resist film with use of a developer solution, and measurement data of the resist pattern is acquired; and a step 3 in which the measurement data and the reference data are compared so as to determine whether or not the difference is within the acceptable range. With respect to this method for verifying a photosensitive composition, the developer solution is an organic solvent type developer solution that contains an aliphatic hydrocarbon solvent, an aromatic hydrocarbon, and at least one kind of metal atoms that are selected from the group consisting of Al atoms, Fe atoms and Ni atoms; and the mass ratio of the content of the aromatic hydrocarbon to the content of the metal atoms in the developer solution is 5.0 × 104 to 2.0 × 1010.

Description

Technical Field

[0001] The present invention relates to a method for assaying a photosensitive composition and a method for producing a photosensitive composition, which contain a photoacid generator and a photoacid-decomposable resin having a group that decomposes by the action of an acid to generate a polar group.

Background Art

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), microfabrication by lithography using a photosensitive composition has been performed. In recent years, with the increasing integration of integrated circuits, the formation of ultra-fine patterns in the sub-micron region or quarter-micron region has been required. Along with this, the exposure wavelength has also tended to shorten from g-line to i-line, and further to ArF excimer laser light and KrF excimer laser light. Furthermore, currently, in addition to excimer laser light, lithography using electron beams and EUV (Extreme Ultra Violet) light is also being developed. 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 rays as a light source.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[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, the procedure for forming a resist pattern and measuring the LWR of the formed resist pattern 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 have found that the above problems can be solved by the following configuration. [1] Step 1: Form a resist film on a substrate 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; expose the resist film to light; perform a developing process using a developer to form a resist pattern; and obtain one standard data selected from the group consisting of line width or space width of a line-shaped resist pattern, aperture diameter of openings in the resist pattern, and dot diameter of a dot-shaped resist pattern; Step 2: Form a resist film on a substrate using a measurement photosensitive composition containing the same type of components as those contained in the standard photosensitive composition; expose the resist film to light; perform a developing process using a developer to form a resist pattern; and obtain measurement data of the resist pattern; and Step 3: Compare the standard data with the measurement data to determine whether it is within an acceptable range, wherein the developer is an organic solvent-based developer containing an aliphatic hydrocarbon solvent, an aromatic hydrocarbon, and at least one metal atom selected from the group consisting of Al, Fe, and Ni, and the mass ratio of the content of the aromatic hydrocarbon to the content of the metal atom in the developer is 5.0 × 10 4 ~2.0×10 10 A method for testing photosensitive compositions. [2] A method for testing the photosensitive composition described in [1], wherein the acid-degradable resin has repeating units represented by formula (Y) described later. [3] The method for testing a photosensitive composition according to [1] or [2], wherein the exposure in step 1 and step 2 uses one of the following: KrF excimer laser light, ArF excimer laser light, electron beam, and extreme ultraviolet light. [4] A method for testing a photosensitive composition according to any one of [1] to [3], wherein the aliphatic hydrocarbon solvent is undecane and the developer further contains butyl acetate. [5] The method for testing the photosensitive composition according to [4], wherein the ratio of the content of butyl acetate to the content of undecane is 65 / 35 to 99 / 1. [6] The method for testing the photosensitive composition according to [4], wherein the ratio of the content of butyl acetate to the content of undecane is 90 / 10. [7] A method for testing a photosensitive composition according to any one of [1] to [6], wherein the content of the above aromatic hydrocarbon is 1% by mass or less relative to the total mass of the above developing solution. [8] The above 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) of 2.0 to 5.0 (MPa) based on the Hansen solubility parameter in the above treatment solution. 1 / 2 Furthermore, at least one of the above monomers has a difference in solubility index (ΔR) before and after acid elimination of 5.0 (MPa). 1 / 2 The above is a method for testing a photosensitive composition as described in any of [1] to [7]. [9] A method for testing a photosensitive composition according to any one of [1] to [8], further comprising step 4 of performing a component adjustment of the photosensitive composition for measurement if the measurement data is determined to be outside the acceptable range in step 3 above.

[10] A method for producing a photosensitive composition, comprising a method for testing a photosensitive composition as described in any of [1] to [9]. [Effects of the Invention]

[0006] 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 it exhibits a predetermined LWR. [Brief explanation of the drawing]

[0007] [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 an example of a method for obtaining reference data for the testing method of a photosensitive composition according to an embodiment of the present invention. [Figure 3] This flowchart shows an example of a method for obtaining 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 testing a photosensitive composition according to an embodiment of the present invention. [Figure 5]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]

[0008] 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 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. In this specification, "ppm" means parts-per-million (10 -6 ) means. "ppb" stands for parts-per-billion (10 -9 ) means. "ppt" stands for parts-per-trillion (10 -12 ) means.

[0009] 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".

[0010] 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).

[0011] In this specification, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. Specifically, it is a value obtained by calculation based on the Hammett substituent constant and a database of known literature values using the following software package 1. All the pKa values described in this specification indicate values obtained by calculation using this software package.

[0012] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs).

[0013] On the other hand, pKa can also be determined by a molecular orbital calculation method. As a specific method, there is a method of calculating by calculating the dissociation free energy of H in an aqueous solution based on a thermodynamic cycle. + Regarding the calculation method of the dissociation free energy of H, for example, it can be calculated by DFT (density functional theory), but various other methods have been reported in the literature and the like, and it is not limited to this. Although there are multiple software that can perform DFT, for example, Gaussian16 can be mentioned. +

[0014] As described above, the pKa in this specification refers to a value obtained by calculation based on the Hammett substituent constant and a database of known literature values using software package 1. However, if pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional theory) shall be adopted.

[0015]

[0016] In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0016] The inventors have found that by comparing reference data and measurement data regarding a predetermined pattern size obtained from resist patterns formed using two photosensitive compositions containing the same type of component, it is possible to determine whether the photosensitive compositions exhibit similar performance in terms of LWR (low wave resistance). Specifically, when using an organic solvent-based developer containing aliphatic hydrocarbon solvents, aromatic hydrocarbons, and specific metal atoms, with the aromatic hydrocarbon / specific metal atom content ratio being within a predetermined range, we found a correlation between the differences between predetermined pattern sizes and the differences between LWRs. In other words, we found that when the predetermined pattern sizes are similar, the LWR performance is also similar, while when the predetermined pattern sizes are different, the LWR performance is also different. When using a conventional developer with two photosensitive compositions containing the same type of components, the pattern size results and the LWR results can vary significantly. In contrast, when using the developer of the present invention with two photosensitive compositions containing the same type of components, both the variation in the predetermined pattern size results and the variation in the LWR results are small. Furthermore, when comparing the results for a predetermined pattern size, it was found that the LWR performance was comparable. Although the detailed reasons why both the amplitude of the resulting pattern size and the amplitude of the LWR can be suppressed are still unknown, the inventors speculate that when the mass ratio of aromatic hydrocarbons to the content of specific metal atoms is within a predetermined range, when forming a resist pattern using the above developer, both the decrease in resolution due to aromatic hydrocarbons and the decrease in pattern shape due to specific metal atoms can be suppressed, thereby suppressing the amplitude of the pattern size originating from the developer, and as a result, the LWR also becomes stable. The following provides a detailed explanation of the testing method for photosensitive compositions.

[0017] [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 an example of a method for obtaining reference data for the method for testing a photosensitive composition according to an embodiment of the present invention, and Figure 3 is a flowchart showing an example of a method for obtaining measurement data for the method for testing a photosensitive composition according to an embodiment of the present invention.

[0018] 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 it is determined to be within an acceptable range, it is determined to be a photosensitive composition exhibiting a predetermined LWR. On the other hand, if it is determined in step 3 (step S14) that the composition falls outside the acceptable range, it is determined to be a photosensitive composition that does not exhibit a predetermined LWR. Thus, this method for testing photosensitive compositions allows for easy determination of whether a photosensitive composition exhibits a predetermined LWR (Line Width Roughness).

[0019] Step 1 (Step S10) for acquiring reference data includes the following steps. The various materials used in this process will be described in detail later.

[0020] In step 1 (step S10) shown in Figure 2, a resist film is first formed on a substrate 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 (step S20). The substrate is not particularly limited, and semiconductor substrates such as silicon substrates can be used. The method for forming the resist film is not particularly limited, and for example, it can be formed using a spin coater. In forming the resist film, after coating the substrate with a reference photosensitive composition, a pre-baking treatment may be performed on the coating of the reference photosensitive composition.

[0021] Next, the formed resist film is subjected to pattern exposure (step S21). In pattern exposure, the resist film is exposed with light of a wavelength corresponding to the photosensitive composition. As the exposure light, 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 step S21 is not particularly limited and may include, for example, a line pattern (line and space), a hole pattern, and a dot pattern. When the photosensitive composition is of the positive type, the pattern used for pattern exposure is a pattern having shapes such as holes, trenches, and lines, in which the exposed areas of the resist film are removed by development. When the photosensitive composition is of the negative type, the pattern used for pattern exposure has shapes such as dots and lines, and the exposed areas of the resist film remain after development.

[0022] Next, the resist film on the substrate is developed using a developer to form a resist pattern (step S22). The method for developing the resist film is not particularly limited as long as it uses the developer of the present invention, and the developer may be applied to the resist film in atomized form, or the resist film may be immersed in the developer.

[0023] Next, the resist pattern formed in step S22 is measured to determine a predetermined pattern size (step S23). The pattern size measured in step S23 is one of the sizes selected from the group consisting of the line width or space width of a linear resist pattern, the opening diameter of an opening in the resist pattern, and the dot diameter of a dot-shaped resist pattern (hereinafter also referred to as the "specific pattern size"). The specific pattern size measured in step S23 is expressed in units of, for example, nm. The specific pattern size can be measured using a scanning electron microscope (SEM), such as the "CG-4100" manufactured by Hitachi High-Tech Corporation. For example, in the case of a linear resist pattern, the linear resist pattern formed in step S22 is observed using an SEM, the line width is measured at any 96 points in the observed image, and the line width of the linear resist pattern can be obtained by arithmetic mean of the obtained measurements. In this way, a specific pattern size of the resist pattern is obtained as reference data (step S10).

[0024] Step 2 (Step S12) for acquiring measurement data includes the following steps. In step 2 (step S12) shown in Figure 3, a resist film is first formed on the substrate using a photosensitive composition for measurement that contains the same type of components as those contained 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 formed resist film is subjected to pattern exposure (step S31). The method for pattern exposure of the resist film is as described in step S21 above. It is preferable that the exposure pattern and exposure conditions are the same in step S21 and step S31. Next, the resist film on the substrate is developed using a developer to form a resist pattern (step S32). The method for developing the resist film in step S32 is as described in step S22 above, and it is preferable that it is the same as the development method in step S22 above. Next, the specific pattern size of the resist pattern formed in S32 is measured (step S33). In step S33, the specific pattern size is measured in the same manner as in step S23. The specific pattern size measured in step S33 is expressed in units of, for example, nm. In this way, the specific pattern size of the resist pattern is obtained as measurement data (step S12).

[0025] In order to compare the reference data and the measurement data in step S14 (process 3), which will be described later, the reference data acquired in step S10 and the measurement data acquired in step S12 will be in the same data format. By using the same data format, it becomes easier to compare the reference data and the measurement data. As described above, in step S14 (step 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, for example, by the difference ΔP expressed as {(measured data)-(reference data)}. In step 3, the acceptable range is the difference ΔP between the measurement data and the reference data for the specific pattern size, for example, -1.0 to 1.0 nm, preferably -0.5 to 0.5 nm, and more preferably -0.3 to 0.3 nm. However, the acceptable range in step 3 is not limited to the above range and can be set appropriately depending on the composition and application of the photosensitive composition, as well as the evaluation conditions.

[0026] [Second example of a method for testing photosensitive compositions] Figure 4 is a flowchart showing a second example of a method for testing a photosensitive composition according to an embodiment of the present invention. Note that in the second example of the method for testing a photosensitive composition shown in Figure 4, a detailed explanation of the steps identical to 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), a step 4 (step S16) is performed in which the reference data and the measurement data are compared, and if the measurement data is determined to be outside the acceptable range, the components of the photosensitive composition for measurement are adjusted. On the other hand, if the measurement data is determined to be within an acceptable range in step S14 (process 3), no component adjustment is performed. In addition, in step S14 (step 3), step 4 (step S16), in which the components of the photosensitive composition for measurement are adjusted, may be repeated until the measurement data is determined to be within an acceptable range. The photosensitive composition for measurement contains the same types of 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. After adjusting the components of the photosensitive composition for measurement in step S16, the process may return to step S12 and acquire measurement data again.

[0027] [An example of a method for producing a photosensitive composition] Figure 5 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 producing the photosensitive composition shown in Figure 5, 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 the reference data and the measurement data are compared, and if the measurement data is determined to be within an acceptable range, the photosensitive composition for measurement is determined to be a good product. The good product is the photosensitive composition product. On the other hand, step S14 (step 3) includes a step (step S42) in which the reference data and the measurement data are compared, and if the measurement data is determined to be outside the acceptable range, the photosensitive composition for measurement is judged to be a defective product. The defective product is not included in the final product.

[0028] 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 as step 4 (step S16) of 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 S44) may be repeated until the measurement data is determined to be within an acceptable range. After adjusting the components of the photosensitive composition for measurement in step S44, the process may return to step S12 and acquire measurement data again.

[0029] 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.

[0030] Although the method for testing the photosensitive composition and the method for producing the 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.

[0031] [Developer] The developer used in the assay method of the present invention is an organic solvent-based developer containing an aliphatic hydrocarbon solvent, an aromatic hydrocarbon, and at least one metal atom selected from the group consisting of Al, Fe, and Ni (hereinafter also referred to as "specific metal atom"), wherein the mass ratio of the aromatic hydrocarbon content to the specific metal atom content in the organic solvent is 5.0 × 10⁻⁶. 4 ~2.0×10 10 That is the case. The following details the components contained in the developing solution.

[0032] <Organic solvents> In this specification, "organic solvent-based developer" means a developer in which the organic solvent content is 80% by mass or more of the total mass of the developer. In this specification, aromatic hydrocarbons are not included in the above organic solvents. The organic solvent contained in the developer may be a single type or a mixture of two or more solvents. At least one of the organic solvents contained in the developer is an aliphatic hydrocarbon solvent. Hereafter, the term "developer" will be interpreted as including the meaning of "organic solvent-based developer."

[0033] Aliphatic hydrocarbon solvents The developing solution contains an aliphatic hydrocarbon solvent. "Aliphatic hydrocarbon solvent" refers to an organic solvent composed of aliphatic hydrocarbons, and "aliphatic hydrocarbon" refers to a hydrocarbon consisting only of hydrogen atoms and carbon atoms and lacking 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.

[0034] 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.

[0035] The aliphatic hydrocarbon solvent 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 developer. 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.

[0036] Ester-based solvents The developer 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 even more preferably 7 or less. Specifically, the number of carbon atoms in the ester solvent is preferably 6.

[0037] 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, ethyl acetate, and hexyl acetate, and more preferably contains butyl acetate.

[0038] The ester solvent content 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 developer. 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.

[0039] The developer preferably contains an aliphatic hydrocarbon and an ester solvent, more preferably consists only of an aliphatic hydrocarbon and an ester solvent, and even more preferably consists only of undecane and butyl acetate. When the developer contains an aliphatic hydrocarbon and an ester solvent, 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 developer. 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.

[0040] <<Other Solvents>> The developing solution may contain other solvents in addition to those mentioned above. Other solvents include, for example, ketone-based solvents, amide-based solvents, and ether-based solvents.

[0041] 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, relative to the total mass of the developer. The upper limit is often less than 100% by mass, relative to the total mass of the developer. Methods for measuring the content of organic solvents include, for example, methods using GC (gas chromatography) and methods using GC-MS (gas chromatography-mass spectrometry).

[0042] <Aromatic hydrocarbons> The developing 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 developer. If the aromatic hydrocarbon contains two or more types of aromatic hydrocarbons, it is preferable that the total content of the two or more aromatic hydrocarbons is within the above range.

[0043] 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.

[0044] Aromatic hydrocarbons are C 10 H 14 , C 11 H 16 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.

[0045] [ka]

[0046] In formula (c), R c represents a substituent. c represents an integer from 0 to 6.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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-methybutyl)-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.

[0051] Aromatic hydrocarbons may be used individually or in combination of two or more. The developer 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 aromatic hydrocarbons. One example of a method for measuring the content of aromatic hydrocarbons is the method for measuring the content of organic solvents described above. 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.

[0052] <Specific metal atoms> The developer contains at least one metal atom selected from the group consisting of Al, Fe, and Ni. In this specification, these metal atoms contained in the developer are metal atoms that may be present in a resist composition in normal operation. In this specification, "content of specific metal atoms" means the total content of the specified metal atoms. The form of the metal atoms contained in the developer is not particularly limited and may be in the form of compounds such as salts, in elemental form, or in ionic form. When metal atoms exist in elemental form, they may exist in particulate form.

[0053] Specific metal atoms may be used individually or in combination of two or more types. The content of specific metal atoms is preferably 0.001 to 50,000 ppts by mass, more preferably 0.01 to 1,000 ppts by mass, and even more preferably 0.1 to 50 ppts by mass, relative to the total mass of the developer. If the developer contains two or more metals, it is preferable that the total content of these 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 the specific metal atoms is 0.01 to 100 ppt by mass relative to the total mass of the developer.

[0054] The developer used in the assay method of the present invention has a mass ratio of aromatic hydrocarbon content to specific metal atom content (aromatic hydrocarbon content / specific metal atom content) of 5.0 × 10⁻⁶ 4 ~2.0×10 10 Therefore, 3.0 × 10 5 ~1.0×10 9 Preferably, 3.0 × 10 5 ~2.5×10 8 This is preferable. Examples of known methods for measuring the content of specific metal atoms include ICP-MS (ICP mass spectrometry). Methods for adjusting the content of the specified metal atoms include, for example, filtering using the above-mentioned filter, selecting raw materials with a low content of the specified metal atoms as raw materials constituting the various components, distilling under conditions that suppress contamination by lining the inside of the apparatus with Teflon®, etc., and adding the specified metal atoms or compounds containing the specified metal atoms.

[0055] [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. 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.

[0056] <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").

[0057] The following details the repeating units contained in acid-degradable resins.

[0058] ≪Repeating units with acid-degradable groups (Aa)≫ The resin (A) preferably has repeating units (Aa) having acid-degradable groups (hereinafter also referred to as "repeating units (Aa)"). 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.

[0059] 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.

[0060] 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)

[0061] 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.

[0062] 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, as described later, 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.

[0063] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0064] [ka]

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] As the repeating unit (Aa), the repeating unit represented by formula (A) is also preferred.

[0071] [ka]

[0072] 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.

[0073] 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.

[0074] 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.

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

[0076] [ka]

[0077] 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).

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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).

[0083] 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).

[0084] 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).

[0085] [ka]

[0086] 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.

[0087] ≪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.

[0088] 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.

[0089] [ka]

[0090] 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).

[0091] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] 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.

[0096] 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 such embodiments, the content of repeating units having acidic groups in resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%, relative to the total repeating units in resin (A).

[0097] ≪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.

[0098] 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.

[0099] 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.

[0100] 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).

[0101] [ka]

[0102] 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.

[0103] ≪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.

[0104] ≪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.

[0105] <<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, bisulfonylimide groups, and aliphatic alcohol groups with the α-position substituted 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.

[0106] ≪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.

[0107] 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.

[0108] 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, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0109] ≪Properties of Resin (A)≫ One preferred embodiment of the acid-degradable resin is one in which the acid-degradable resin has repeating units derived from monomers having acid-degradable groups, all of which have a solubility index (R) of 2.0 to 5.0 based on the Hansen solubility parameter in a developer, represented by formula (1) described later, and at least one of the monomers has a difference (ΔR) of the solubility index (R) before and after acid desorption of 4.0 or more. Below, we will first explain the above characteristics.

[0110] One way to identify resins with desired properties is to use Hansen solubility parameters. Hansen solubility parameters divide the solubility of a substance into three components (dispersion term δd, polarity term δp, and hydrogen bonding term δh) and represent 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.

[0111] 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.

[0112] In the above testing method, the above Hansen solubility parameter can be used, and a resin (A) consisting of structural units (or monomers) located at a certain distance from the developer, based on the coordinates which are the Hansen solubility parameters of the developer, can be used, assuming that such structural units dissolve appropriately in the developer. In other words, the dispersion term of the Hansen solubility parameter of the developer 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 developer, shown in equation (1), is used as the dissolution index for each monomer that induces the structural units constituting the resin (hereinafter sometimes 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 developer. δp2 represents the polarity term in the Hansen solubility parameter of the above-mentioned developer. δh2 represents the hydrogen bonding term in the Hansen solubility parameter of the above-mentioned developer. The δd2, δp2, or δh2 of the developer solution is determined by multiplying the δd2, δp2, or δh2 of the solvent components (e.g., aromatic hydrocarbons, organic solvents) contained in the developer solution by the content of the solvent components and summing the results.

[0113] In resin (A), all monomers having acid-degradable groups have a solubility index (R) of 2.0 to 5.0 (MPa). 1 / 2 Preferably, the pressure is 2.1 to 4.9 (MPa). 1 / 2 It is more preferable that the pressure be 2.2 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) is a monomer having an acid-degradable group, and the difference in solubility index (R) before and after acid elimination (solubility index difference (△R)) is 4.0 (MPa). 1 / 2 Preferably, the structural unit is derived from the above monomer, and has a solubility index difference (ΔR) of 5.0 (MPa). 1 / 2 It is more preferable that the structural unit is derived from the monomers described above. There is no particular upper limit to the above ΔR, but 10.0 (MPa) 1 / 2 The following are common cases.

[0114] Preferably, the resin (A) is composed 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. Preferably, the amount of repeating units derived from acrylate monomers is 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%, more preferably 40 to 100 mol%, and even more preferably 50 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] Regarding hydrophobic resin (E), see paragraph

[0348] of Japanese Patent Publication No. 2014-010245. Refer to the description in

[0415] , and these contents are incorporated herein. 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 the composition was 2.0 mass%.

[0144] [Table 1]

[0145] Acid-degradable resins A-1 and A-2 are resins obtained by radical polymerization of monomers represented by the following formulas, and are resins having repeating units derived from each monomer. The content, molecular weight, and degree of dispersion of each repeating unit are shown in Table 2. Table 2 also shows the solubility index (R) of the following monomers B and C that have acid-degradable groups. B and R C ) and the difference in solubility index (ΔR B and ΔR C ) indicates.

[0146] [ka]

[0147] [Table 2]

[0148] [ka]

[0149] [ka]

[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 the developing solution] The developers for the examples and comparative examples were prepared by mixing the components and their respective contents as shown in the table below. The content of the specific metal atom was adjusted by passing the developer prepared for the filter through until it reached a predetermined content, or by adding each specific metal. The content of the aromatic hydrocarbon was adjusted by applying the above-described method for adjusting the content of the aromatic hydrocarbon to raw materials such as the following organic solvents used in the preparation of the developer. Also, the water content in each developer was adjusted to be 20 to 1000 mass ppm with respect to the total mass of each developer. The content of each component was calculated from the charged amount or measured using the above-described measurement methods for the content of each component. In each developer, the content of the organic solvent constitutes the remainder other than the components and water described in the table to be described later.

[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 the following table, each description indicates the following. The "content (a)" column of "organic solvent" indicates the content mass of the aliphatic hydrocarbon when the total mass of the organic solvent is 100. The "content (b)" column of "organic solvent" indicates the content mass of the ester solvent when the total mass of the organic solvent is 100. Therefore, for example, the developer 1 has a mass ratio of aliphatic hydrocarbon to ester solvent of 10:90. The "total (c)" column of "aromatic hydrocarbon" indicates the total content (mass ppm) of aromatic hydrocarbons C1 - C4 with respect to the total mass of the developer. The columns of "C1" to "C4" of "aromatic hydrocarbon" indicate the respective contents (mass ppm) of aromatic hydrocarbons C1 - C4 with respect to the total mass of the developer. The "total (e)" column of "specific metal atoms" indicates the total content (mass ppt) of three metals, Fe, Ni, and Al, with respect to the total mass of the developer. The columns of "Fe", "Ni", and "Al" of "specific metal atoms" indicate the respective contents (mass ppt) of Fe, Ni, and Al with respect to the total mass of the developer. The column of "(c) / (e)" indicates the mass ratio of the content of aromatic hydrocarbon to the content of specific metal atoms (content of aromatic hydrocarbon / content of specific metal atoms (total content of the above - mentioned specific metals)). Also, "E + n" means "×10 n ", and n represents an integer of 0 or more. Specifically, "1.50E + 10" means "1.50×10 10 ". Note that the above "E + n" has the same meaning in other columns.

[0156]

Table 3

[0157] [Example 1] <Test 1> (Test 1 - 1 (Step 1)) On a 12 - inch silicon wafer, a composition AL412 (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. On top of it, Composition 1 prepared above was applied and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 50 nm. Thus, a silicon wafer having a resist film was fabricated. A silicon wafer having the obtained resist film was subjected to pattern exposure using an EUV lithography system (ASML NXE3400, NA 0.33, Quadrupole, outer sigma 0.885, inner sigma 0.381). A photomask with a line width of 35 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 paddle with developer solution 1 for 30 seconds, and the wafer was rotated at a speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 70 nm. The obtained resist pattern was measured for line width using a SEM (Hitachi High-Tech Corporation's "CG-4100"), and the line width (P1) was obtained. Furthermore, using the same resist pattern, the resist pattern was observed from the normal direction of the wafer surface using the above-mentioned SEM, and the line widths at 96 arbitrary locations were measured. From the obtained line width data, a value three times the standard deviation σ (3σ) was calculated, and the LWR(L1) was obtained.

[0158] (Test 1-2 (Process 2)) Next, the same procedure as above was repeated using composition 1. Specifically, composition AL412 (manufactured by Brewer Science) for forming the underlayer film was applied to a 12-inch silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. Composition 1 prepared above was then applied on top of this and baked (PB) at 120°C for 60 seconds to form a resist film with a thickness of 50 nm. This resulted in the fabrication of a silicon wafer with a resist film. A silicon wafer having the obtained resist film was subjected to pattern exposure using an EUV lithography system (ASML NXE3400, NA 0.33, Quadrupole, outer sigma 0.885, inner sigma 0.381). A photomask with a line width of 35 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 paddle with developer solution 1 for 30 seconds, and the wafer was rotated at a speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 70 nm. The obtained resist pattern was measured for line width using a SEM (Hitachi High-Tech Corporation's "CG-4100"), and the line width (P2) was obtained. Furthermore, using the same resist pattern, the resist pattern was observed from the normal direction of the wafer surface using the above-mentioned SEM, and the line widths at 96 arbitrary locations were measured. From the obtained line width data, three times the standard deviation σ (3σ) was calculated, and the LWR(L2) was obtained.

[0159] As described above, the procedure of pattern exposure of a resist film formed using composition 1, followed by development with developer solution 1, and then measuring the line width of the resulting resist pattern was repeated twice. As a result, the line width (P1) of the first measurement was 35.0 nm, and the line width (P2) of the second measurement was 35.2 nm, with both results being almost identical. The difference in line width (line width of the second measurement (P2) - line width of the first measurement (P1)) was 0.2 nm. Furthermore, LWR measurements were performed on each of the two resist patterns formed using composition 1. As a result, the LWR (L1) of the first measurement was 3.0 nm, and the LWR (L2) of the second measurement was 3.1 nm, with the results being almost identical. The difference in LWR (LWR (L2) of the second measurement - LWR (L1) of the first measurement) was 0.2 nm.

[0160] <Exam 2> The test was conducted using the same procedure as in <Test 1> (Test 1-2) above, except that composition 2 was used instead of composition 1. The resist film formed using composition 2 was pattern-exposed, then developed with developer 1, and the line width of the resulting resist pattern was measured. This procedure was repeated twice. As a result, the line width (P1) for the first measurement was 35.0 nm, and the line width (P2) for the second measurement was 36.2 nm. The difference in line width (second line width (P2) - first line width (P1)) was 1.2 nm, which was a larger value compared to the case of <Test 1> described above. Furthermore, the LWR(L1) obtained when the first pattern formation was performed using composition 1 was 3.0 nm, and the LWR(L2) obtained when the second pattern formation was performed using composition 2 was 3.6 nm. The difference in LWR (2nd LWR(L2) - 1st LWR(L1)) was 0.6 nm, which was a larger value compared to the case of <Test 1> described above.

[0161] The results of the above-mentioned <Test 1> and <Test 2> confirmed that when the difference in line width was small, the difference in LWR was also small, and when the difference in line width was large, the difference in LWR was also large. This result demonstrates that the measured line width is closely correlated with the evaluation result of LWR. Based on the above results, for example, if the line width difference is set to within -0.5 to 0.5 nm as the acceptable range, and the test is performed according to the method described in (Test 1-2) above, except that a different photosensitive composition is used instead of composition 1 used in (Test 1-2) of <Test 1>, then if the line width difference of the resulting resist pattern is within the acceptable range, it can be determined that the LWR result of the resist pattern formed using the different photosensitive composition will be similar to that of the resist pattern formed using composition 1.

[0162] [Example 2] The experiment was conducted using the same procedure as in Example 1, except that developer 2 was used instead of developer 1. The results are shown in Table 4, and, as in Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results. [Example 3] An experiment was conducted in the same procedure as in Example 1, except that developer 5 was used instead of developer 1. The results are shown in Table 4. Similar to Example 1, it was demonstrated that the measured line width was closely correlated with the evaluation result of LWR. [Example 4] An experiment was conducted in the same procedure as in Example 1, except that developer 6 was used instead of developer 1. The results are shown in Table 4. Similar to Example 1, it was demonstrated that the measured line width was closely correlated with the evaluation result of LWR.

[0163] [Comparative Example 1] When an experiment was conducted in the same procedure as <Test 2> of [Example 1] using developer 3 instead of developer 1, as shown in Table 4, the line width after the operation of removing the resist film formed using Composition 2 with developer 3 was 35.2 nm, and the LWR result when the second pattern formation using Composition 2 was performed was 4.0 nm. As shown in Table 4, in this Comparative Example 1, although the difference in line width (second line width (P2) - first line width (P1)) was close to 0.2 nm, the difference ((L2)-(L1)) between the LWR (L1) when the first pattern formation using Composition 1 was performed and the LWR (L2) when the second pattern formation using Composition 2 was performed was as large as 1.0 nm, and there was no correlation between the difference in line width and the difference in LWR. From this result, it was confirmed that the photosensitive composition cannot be tested when it is not the predetermined developer.

[0164] [Comparative Example 2] When an experiment was conducted in the same procedure as <Test 2> of [Example 1] using developer 4 instead of developer 1, as shown in Table 4, the line width after the operation of removing the resist film formed using Composition 2 with developer 3 was 34.8 nm, and the LWR result when the second pattern formation using Composition 2 was performed was 4.2 nm. As shown in Table 4, in this Comparative Example 2, despite the line width difference (second line width (P2) - first line width (P1)) being close at -0.2 nm, the difference between the LWR (L1) when the first pattern was formed using composition 1 and the LWR (L2) when the second pattern was formed using composition 2 ((L2) - (L1)) 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 a developer other than the specified one is used.

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

[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] Developer A1 was prepared, which had the same composition as Developer 1 except that the mass ratio of undecane to butyl acetate (undecane:butyl acetate) was 5:95. The experiment was carried out using the same procedure as in Example 1, except that Developer A1 was used instead of Developer 1. Similar to Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results. Similarly, developer A2 was prepared, which had the same composition as developer 1 except that the mass ratio of undecane to butyl acetate (undecane:butyl acetate) was 15:85. Developer A3 had the same composition as developer 1 except that the mass ratio of undecane to butyl acetate (undecane:butyl acetate) was 40:60. Developer A4 had the same composition as developer 1 except that the mass ratio of undecane to butyl acetate (undecane:butyl acetate) was 60:40. The experiment was conducted using the same procedure as in Example 1, except that developers A2 to A4 were used instead of developer 1. As in Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results.

[0169] Developer B1 was prepared, which had the same composition as developer 1 except that decane was used instead of undecane. Developer B2 was also prepared, which had the same composition as developer 1 except that dodecane was used instead of undecane. The experiment was conducted using the same procedure as in Example 1, except that developers B1 and B2 were used instead of developer 1. As in Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results. Furthermore, developer B3, which has the same composition as developer 1 except that amyl acetate is used instead of butyl acetate, and developer B4, which has the same composition as developer 1 except that isoamyl formate is used instead of butyl acetate, were prepared. When the experiment was carried out in the same procedure as in Example 1, except that developers B3 and B4 were used instead of developer 1, it was demonstrated that, as in Example 1, the measured line width was closely correlated with the LWR evaluation result.

[0170] Developer C1 was prepared, which had the same composition as developer 2 except that decane was used instead of undecane. Developer C2 was also prepared, which had the same composition as developer 2 except that dodecane was used instead of undecane. The experiment was conducted using the same procedure as in Example 2, except that developers C1 and C2 were used instead of developer 2. As in Example 2, it was demonstrated that the measured line width closely correlated with the LWR evaluation results. Furthermore, developer C3, which has the same composition as developer 2 except that amyl acetate is used instead of butyl acetate, and developer C4, which has the same composition as developer 2 except that isoamyl formate is used instead of butyl acetate, were prepared. When the experiment was carried out in the same procedure as in Example 2, except that developers C3 and C4 were used instead of developer 2, it was demonstrated that, as in Example 2, the measured line width was closely correlated with the LWR evaluation results.

[0171] Developer D1 was prepared, which had the same composition as developer 3 except that decane was used instead of undecane. Developer D2 was also prepared, which had the same composition as developer 3 except that dodecane was used instead of undecane. The experiment was conducted using the same procedure as in Comparative Example 1, except that developers D1 and D2 were used instead of developer 3. Similar to Comparative Example 1, there was no correlation between the difference in line width and the difference in LWR. Furthermore, developer D3, which has the same composition as developer 3 except that amyl acetate is used instead of butyl acetate, and developer D4, which has the same composition as developer 3 except that isoamyl formate is used instead of butyl acetate, were prepared. When the experiment was carried out in the same procedure as in Comparative Example 1, except that developer D3 and D4 were used instead of developer 3, there was no correlation between the difference in line width and the difference in LWR, similar to Comparative Example 1.

[0172] Developer E1, which has the same composition as developer 4 except that decane was used instead of undecane, and developer E2, which has the same composition as developer 4 except that dodecane was used instead of undecane, were prepared. When the experiment was carried out in the same procedure as in Comparative Example 2, except that developers E1 and E2 were used instead of developer 4, there was no correlation between the difference in line width and the difference in LWR, similar to Comparative Example 2. Furthermore, developer E3, which has the same composition as developer 4 except that amyl acetate is used instead of butyl acetate, and developer E4, which has the same composition as developer 4 except that isoamyl formate is used instead of butyl acetate, were prepared. When the experiment was carried out in the same procedure as in Comparative Example 2, except that developer E3 and E4 were used instead of developer 4, there was no correlation between the difference in line width and the difference in LWR, similar to Comparative Example 2.

[0173] The experiment was conducted using the same procedure as in Example 1, except that developer A3, which has the same composition as developer 1 except that the mass ratio of aromatic hydrocarbon content to specific metal atom content (aromatic hydrocarbon content / specific metal atom content) is 2.0E+05, was used instead of developer 1. As in Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results.

[0174] Composition A1 was prepared by the method described in [Preparation of Composition] above, except that acid-degradable resin A-3, obtained by radical polymerization of a monomer represented by the following formula, was used as the acid-degradable resin instead of acid-degradable resin A-1. Table 5 below shows the content, molecular weight, and dispersibility of each repeating unit of acid-degradable resin A-3, as well as the solubility index (R) and solubility index difference (ΔR) of the monomer having an acid-degradable group. The experiment was conducted using the same procedure as in Example 1, except that composition A1 was used instead of composition 1. Similar to Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results.

[0175] [ka]

[0176] [Table 5]

[0177] Furthermore, composition A2 was prepared by the method described in [Preparation of Composition] above, except that acid-degradable resin A-1 was replaced with acid-degradable resin A-3 in a mass ratio of 7:3 (acid-degradable resin A-1: ​​acid-degradable resin A-3). The experiment was conducted using the same procedure as in Example 1, except that composition A2 was used instead of composition 1. Similar to Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results.

[0178] Composition A3 was prepared by the method described in [Preparation of Composition] above, except that photoacid generator B-2, represented by the following formula, was used instead of photoacid generator B-1. The experiment was carried out using the same procedure as in Example 1, except that composition A3 was used instead of composition 1, and it was demonstrated that, as in Example 1, the measured line width was closely correlated with the LWR evaluation result.

[0179] [ka]

[0180] Furthermore, composition A4 was prepared by the method described in [Preparation of Composition] above, except that photoacid generator B-1 was replaced with photoacid generator B-2 in a mass ratio of 7:3 (photoacid generator B-1:photoacid generator B-2). The experiment was conducted using the same procedure as in Example 1, except that composition A4 was used instead of composition 1. Similar to Example 1, it was demonstrated that the measured line width closely correlated with the LWR evaluation results. [Explanation of Symbols]

[0181] S10, S12, S14, S16, S20, S21, S22, S24 Step Steps S30, S31, S32, S34, S40, S42, S44

Claims

1. Step 1 involves forming a resist film on a substrate using a standard photosensitive composition containing an acid-degradable resin having a group that decomposes to produce polar groups upon the action of an acid, and a photoacid generator; exposing the resist film to light; developing it using a developer to form a resist pattern; and obtaining one pattern size selected from the group consisting of the line width or space width of a line-shaped resist pattern, the aperture diameter of an opening in the resist pattern, and the dot diameter of a dot-shaped resist pattern as standard data for the resist pattern. Step 2 involves forming a resist film on a substrate using a measurement photosensitive composition containing the same type of components as those contained in the reference photosensitive composition, exposing the resist film to light, performing a development process using a developer to form a resist pattern, and obtaining a pattern size of the same type as the pattern size obtained as the reference data for the resist pattern as 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 developer is an organic solvent-based developer containing an aliphatic hydrocarbon solvent, an aromatic hydrocarbon, and at least one metal atom selected from the group consisting of Al, Fe, and Ni. The mass ratio of the aromatic hydrocarbon content to the metal atom content in the developer is 5.0 × 10 ４ ~2.0 x 10 １０ And, The exposure pattern and exposure conditions are the same for the exposure of the resist film in step 1 and the exposure of the resist film in step 2. A method for testing a photosensitive composition, wherein the developing solution and developing method are the same in the developing process in step 1 and the developing process in step 2.

2. A method for testing a photosensitive composition according to claim 1, wherein the acid-degradable resin has repeating units represented by the following formula (Y). 【Chemistry 1】 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 containing an oxygen atom. 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 multiple Rs are present, they may be the same or different. If multiple Rs are present, they may be bonded to each other to form a ring. 'a' represents an integer between 1 and 3. b represents an integer between 0 and (5-a).

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

4. The aliphatic hydrocarbon solvent is undecane. The developer further contains butyl acetate. A method for testing a photosensitive composition according to any one of claims 1 to 3.

5. The method for testing a photosensitive composition according to claim 4, wherein the ratio of the content of butyl acetate to the content of undecane is 65 / 35 to 99 / 1.

6. The method for testing a photosensitive composition according to claim 4, wherein the ratio of the content of butyl acetate to the content of undecane is 90 / 10.

7. A method for testing a photosensitive composition according to any one of claims 1 to 6, wherein the content of the aromatic hydrocarbon is 1% by mass or less with respect to the total mass of the developer.

8. 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 describes the method for testing a photosensitive composition according to any one of claims 1 to 7. 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.

9. A method for testing a photosensitive composition according to any one of claims 1 to 8, further comprising a step 4 in which, if the measurement data is determined to be outside the acceptable range in step 3, the components of the photosensitive composition for measurement are adjusted.

10. A method for producing a photosensitive composition, comprising a method for testing a photosensitive composition according to any one of claims 1 to 9.

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