Inspection method, method for producing actinic ray-sensitive or radiation-sensitive composition, and method for producing electronic device

Abstract

The present invention provides an inspection method with which minute foreign substances in an actinic ray-sensitive or radiation-sensitive resin composition are easily measured. The present invention also provides a method for manufacturing a composition and a method for manufacturing an electronic device, in which the abovementioned inspection method is used. This method for inspecting an actinic ray-sensitive or radiation-sensitive resin composition containing an alkali-soluble component comprises a step X1 of forming a coating film by coating a substrate with the abovementioned composition, a step X2 of removing the coating film from the substrate using an alkali developer without performing an exposure process using irradiation with active light rays or radioactive rays, and a step X3 of using a defect inspection device to measure the number of defects on the substrate after the coating film has been removed.

Description

[Technical Field]

[0001] The present invention relates to an inspection method, a method for producing an actinic ray-sensitive or radiation-sensitive composition, and a method for producing an electronic device. [Background technology]

[0002] 2. Description of the Related Art It is known that semiconductor devices are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film obtained using an actinic ray- or radiation-sensitive composition (hereinafter also referred to as a "resist composition") is formed on a substrate, and then the resist film is subjected to various treatments such as an exposure treatment in which light is irradiated, a development treatment using a developer, and, if necessary, a rinsing treatment using a rinse solution, thereby obtaining a patterned resist film.The patterned resist film thus obtained is used as a mask to perform various treatments to form an electronic circuit pattern. In order to further improve the yield of semiconductor devices obtained in such semiconductor device fabrication processes, a pattern formation method that can suppress the occurrence of defects is required. In recent years, with the manufacturing of semiconductor devices with a node of 10 nm or less being considered, this trend has become even more pronounced.

[0003] Incidentally, one of the causes of defects in a pattern is foreign matter contained in the resist composition. Conventional methods for inspecting the presence and quantity of foreign matter contained in a resist composition include a method of measuring foreign matter in the resist composition (solution) using a liquid particle counter (e.g., a particle counter manufactured by Rion Co., Ltd., Liquid Particle Counter KS-41B, etc.), and a method of applying the resist composition to a substrate to form a coating film, and then observing this coating film with a defect inspection device (e.g., a dark-field defect inspection device SP5 manufactured by KLA-Tencor Corporation, etc.) to measure foreign matter on the film surface and in the film. However, in a method of measuring foreign particles in a resist composition (solution) using a liquid particle counter, due to the detection limit of the instrument, particles with a particle size of 0.1 μm (100 nm) or larger are usually difficult to detect. Furthermore, in a method of measuring foreign particles on the film surface and in the film using a defect inspection device, defects with a size of 40 to 60 nm are usually detected. Therefore, it is difficult to say that these inspection methods have sufficient detection sensitivity to be applied to the manufacturing of recent semiconductor devices with a 10 nm node or smaller.

[0004] Furthermore, the inspection method for detecting foreign matter in the resist composition is not limited to the above-mentioned inspection methods, and various investigations have been conducted up to now. For example, Patent Document 1 discloses a method for detecting gel-like foreign matter that induces pattern defects, which method "includes the steps of spin-coating a photoresist on a semiconductor substrate, exposing the coated photoresist to ultraviolet light, removing the exposed photoresist with an alkaline developer, and irradiating the semiconductor substrate surface from which the photoresist has been removed with laser light and inspecting for the presence or absence of foreign matter from scattered light." Specifically, Patent Document 1 exposes a positive resist film formed from a positive resist composition by exposure and alkaline development to expose the substrate, and measures gel-like foreign matter adhering to the exposed substrate to detect the presence or absence of gel-like material in the resist composition. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 07-280739 Summary of the Invention [Problem to be solved by the invention]

[0006] The present inventors have studied the foreign matter inspection method described in Patent Document 1 and have found that, in the method of Patent Document 1, a substrate defect inspection is performed after a positive resist film is exposed to light and subjected to alkaline development, which may cause a reaction of components in the resist film during exposure, resulting in the risk of the defect components also being modified.In other words, the inspection method in which a substrate defect inspection is performed after a resist film is exposed to light may not have sufficient detection accuracy for foreign matter inspection of a resist composition, and it has become clear that there is room for improvement.

[0007] Furthermore, as mentioned above, the inspection method is also required to exhibit sufficient detection sensitivity (in other words, to be able to measure even minute foreign particles) even when applied to the manufacture of recent miniaturized semiconductor devices.

[0008] Therefore, an object of the present invention is to provide an inspection method for easily measuring minute foreign matters in an actinic ray-sensitive or radiation-sensitive composition. Another object of the present invention is to provide a method for producing an actinic ray-sensitive or radiation-sensitive composition and a method for producing an electronic device using the above-mentioned inspection method. [Means for solving the problem]

[0009] The present inventors have found that the above problems can be solved by the following configuration.

[0010] [1] A method for inspecting an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component, comprising: A step X1 of applying the composition to a substrate to form a coating film; a step X2 of removing the coating film from the substrate using an alkaline developer without performing an exposure treatment by irradiation with actinic rays or radiation; and a step X3 of measuring the number of defects on the substrate after removing the coating film using a defect inspection device. [2] The inspection method according to [1], further comprising, before step X1, step Y1 of measuring the number of defects on the substrate used in step X1 using a defect inspection device. [3] In the step X1, the substrate is a silicon wafer, and the number of defects measured using a defect inspection device is 0.15 / cm. 2 The testing method according to [1] or [2], which is as follows: [4] In the step X1, the substrate is a silicon wafer, and the number of defects having a size of 20 nm or more on the substrate measured using a defect inspection device is 0.15 / cm 2 The testing method according to any one of [1] to [3], which is as follows: [5] Furthermore, before the above step X2, a step Z1 of applying the alkaline developer used in the step X2 to a substrate; The inspection method according to any one of [1] to [4], further comprising a step Z2 of measuring the number of defects on the substrate coated with the alkaline developer using a defect inspection device. [6] Furthermore, before the step Z1, a step Z3 is performed in which the number of defects on the substrate used in the step Z1 is measured using a defect inspection device; and step Z4 of calculating the number of defects resulting from the alkaline developer used in step Z2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2. [7] The alkaline developer used in the process X2 has a defect size of 0.15 / cm2 or more, as calculated by the following inspection R1. 2 The inspection method according to any one of [1] to [6], wherein the alkaline developer is one of the following: Defect inspection R1: The defect inspection R1 includes the following steps ZA1 to ZA4. Process ZA1: A process of measuring the number of defects on the substrate that are 20 nm or larger in size using a defect inspection device. Step ZA2: applying the alkaline developer to the substrate Step ZA3: A step of measuring the number of defects having a size of 20 nm or more on the substrate coated with the alkaline developer using a defect inspection device. Step ZA4: A step of calculating the number of defects having a size of 20 nm or more resulting from the alkaline developer by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3. [8] The inspection method according to any one of [1] to [7], wherein the alkaline developer is an aqueous solution containing tetramethylammonium hydroxide. [9] The inspection method according to any one of [1] to [8], wherein in step X2, the removal time of the removal treatment using the alkaline developer is 300 seconds or less.

[10] The inspection method according to [9], wherein the removal time is 180 seconds or less.

[11] A method for inspecting an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component, comprising: A step X1 of applying the composition to a substrate to form a coating film; a step X2 of removing the coating film from the substrate using an alkaline developer without performing an exposure treatment by irradiation with actinic rays or radiation; A process X3A of measuring the number of defects on the substrate after removing the coating film using a defect inspection device; Furthermore, before the step X1, a step Y1 of measuring the number of defects on the substrate used in the step X1 using a defect inspection device; Before the above step X2, a step Z1 of applying the alkaline developer used in the step X2 to a substrate; a step Z2 of measuring the number of defects on the substrate coated with the alkaline developer using a defect inspection device; a step Z3 of measuring the number of defects on the substrate used in the step Z1 using a defect inspection device; a step ZX for carrying out a step Z4 for calculating the number of defects resulting from the alkaline developer used in the step X2 by subtracting the number of defects measured in the step Z3 from the number of defects measured in the step Z2; The inspection method described in [1], comprising a step X3E of calculating the number of defects derived from the composition by subtracting the number of defects calculated in the step Y1 and the number of defects calculated in the step Z4 from the number of defects measured in the step X3A.

[12] A step of preparing an actinic ray-sensitive or radiation-sensitive composition; A method for producing an actinic ray-sensitive or radiation-sensitive composition, comprising: a step of carrying out the inspection method according to any one of [1] to

[11] .

[13] A method for manufacturing an electronic device, comprising a step of carrying out the inspection method according to any one of [1] to

[11] . [Effects of the Invention]

[0011] According to the present invention, it is possible to provide an inspection method for simply measuring minute foreign matters in an actinic ray-sensitive or radiation-sensitive composition. Furthermore, the present invention can provide a method for producing an actinic ray-sensitive or radiation-sensitive composition and a method for producing an electronic device using the above-mentioned inspection method. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, when a group (atomic group) is described without specifying whether it is substituted or unsubstituted, it encompasses both unsubstituted and substituted groups, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, the term "organic group" in the present specification refers to a group containing at least one carbon atom. Unless otherwise specified, the substituent is preferably a monovalent substituent. As used herein, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light: Extreme Ultraviolet), X-rays, electron beams (EB), etc. As used herein, "light" refers to actinic rays or radiation. Unless otherwise specified, the term "exposure" in this specification includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet light typified by an excimer laser, extreme ultraviolet light (EUV light), X-rays, etc., but also drawing using particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. The bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "XYZ", Y may be -CO-O- or -O-CO-. In addition, the above compound may be "X-CO-OZ" or "XO-CO-Z".

[0013] In this specification, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, "(meth)allyl" refers to either or both of allyl and methallyl, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0014] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​determined by calculation using this software package.

[0015] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0016] On the other hand, pKa can also be calculated by molecular orbital calculations. This method is based on the thermodynamic cycle and calculates the pKa of H in aqueous solution. + One method is to calculate the dissociation free energy. + The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, such as Gaussian 16.

[0017] As described above, the pKa in this specification refers to a value calculated using the software package 1 based on a database of Hammett's substituent constants and known literature values. However, if the pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be used. Furthermore, as mentioned above, the pKa in this specification refers to the "pKa in aqueous solution," but when the pKa in aqueous solution cannot be calculated, the "pKa in dimethyl sulfoxide (DMSO) solution" will be used.

[0018] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0019] In this specification, the solid content refers to all components other than the solvent. Even if the solid content is in a liquid state, it is counted as the solid content.

[0020] [Testing method] The inspection method of the present invention is a method for inspecting an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component (hereinafter, the "actinic ray-sensitive or radiation-sensitive composition" will also be referred to as a "resist composition"), and includes the following steps X1 to X3. Note that, hereinafter, the "actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component" will also be referred to as the "inspection composition." Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (hereinafter also referred to as "removal solvent") without performing exposure treatment by irradiation with actinic rays or radiation. Step X3: A step of measuring the number of defects on the substrate after removing the coating film using a defect inspection device.

[0021] A feature of the above inspection method is that foreign matter contained in a resist composition (inspection composition) containing an alkali-soluble component is detected on a substrate. The mechanism of action is explained below. In the above-described inspection method, in step X1, the inspection composition is first formed as a coating film on a substrate. In the subsequent step X2, a removal process is performed in which the coating film is removed from the substrate using an alkaline developer (removal solvent). As a result of the removal process, minute foreign particles contained in the coating film (which have particularly strong interactions with the substrate and may cause defects after patterning) may adhere to the surface of the substrate that has undergone step X2 due to, for example, dissolution of the coating film into the alkaline developer. In the inspection method of the present invention, in step X3, the number of defects present on the surface of the substrate that has undergone step X2 is measured. In other words, the inspection method of the present invention detects foreign particles contained in the inspection composition as defects on the substrate. For defects present on the surface of a substrate, such as a silicon wafer used in semiconductor manufacturing, defects of, for example, about 20 nm in size can be measured using a commercially available defect inspection device (e.g., the dark-field defect inspection device SP5 manufactured by KLA-Tencor Corporation). Therefore, compared to the above-mentioned method of measuring foreign matter in a resist composition (solution) using a liquid particle counter (detection limit / measurement target: typically particles with a particle size of 0.1 μm (100 nm) or more), the inspection method of the present invention can detect smaller foreign matter. Furthermore, the inspection method of the present invention can detect smaller foreign matter even compared to the method of measuring foreign matter on the film surface and in the film using a defect inspection device (detection limit / measurement target: typically defects with a size of 40 to 60 nm).

[0022] Therefore, the above-mentioned inspection method allows for easy measurement of minute foreign matters in an actinic ray- or radiation-sensitive composition (test composition). Furthermore, since the above-mentioned inspection method does not involve deterioration of the test composition due to exposure (specifically, deterioration of compounds and defects in the test composition), it can be said to be a technique that is more capable of capturing defects actually contained in the test composition (has superior detection accuracy) than the inspection method of Patent Document 1.

[0023] The inspection method of the present invention will be described below by taking an example of a specific embodiment. Note that, in the following description of the inspection method, an example will be given in which the size of defects measured using a defect inspection device is 20 nm or larger, but the size of the defects is not limited to this. If the detection limit of the device is acceptable, defects smaller than 20 nm may also be inspected.

[0024] [First embodiment of inspection method] The first embodiment of the inspection method is a method for inspecting a resist composition (inspection composition) containing an alkali-soluble component, and includes the following steps X1 to X3. Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (removal solvent) without performing exposure treatment by irradiation with actinic rays or radiation. Step X3: A step of measuring the number of defects on the substrate after removing the coating film using a defect inspection device.

[0025] First, each step will be described below.

[0026] <<Process X1>> Step 1 is a step of forming a coating film on a substrate using a composition (test composition) containing an alkali-soluble component, which is the test target of this testing method. The various materials used in step X1 and the procedure for step X1 will be described below.

[0027] <Various materials> (Test composition) Resist compositions containing alkali-soluble components that can be suitably applied as inspection compositions to this inspection method will be described later.

[0028] (substrate) Substrates include those used in the manufacture of integrated circuit devices, with silicon wafers being preferred. In terms of further improving inspection accuracy, the number of defects on the substrate used in process X1 (number of defects on the original substrate) before applying process X1 is 1.50 / cm 2 Preferably, it is 1.00 pieces / cm or less. 2 More preferably, it is 0.75 pieces / cm or less. 2 More preferably, it is 0.15 pieces / cm or less. 2 It is particularly preferable that the density is equal to or less than 0.00 particles / cm. 2 That's all. In particular, in terms of further improving inspection accuracy, the number of defects of 20 nm or more present on the substrate used in process X1 (number of defects on the original substrate) before application to process X1 is 1.50 / cm 2 Preferably, it is 1.00 pieces / cm or less. 2 More preferably, it is 0.75 pieces / cm or less. 2 More preferably, it is 0.15 pieces / cm or less. 2 It is particularly preferable that the density is equal to or less than 0.00 particles / cm. 2 That's all. If the substrate used in step X1 has a large number of defects, scattering may occur during the defect inspection of the substrate performed in step X3, hindering accurate measurement of the number of defects. For this reason, it is preferable to use a substrate with high cleanliness for the substrate used in step X1, in order to improve the accuracy of the defect inspection in step X3 (and ultimately to further improve the inspection accuracy of this inspection method). The substrate can be inspected for defects by a defect inspection device (for example, a dark field defect inspection device SP5 manufactured by KLA Tencor Corporation).

[0029] <Process X1> Examples of methods for forming a coating film on a substrate using a test composition include a method of applying the test composition to a substrate. Other examples of application methods include a coating method using a coater cup and a coating method using an alkali developing unit. A spin coating method using a spinner is also preferred. The rotation speed during spin coating using a spinner is preferably 500 to 3,000 rpm. After applying the test composition onto the substrate, the substrate is preferably dried. An example of a drying method is a method of drying by heating. Heating can be performed by means of a conventional exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. In one embodiment, heating is preferably performed at 90°C for 90 seconds.

[0030] The thickness of the coating film is not particularly limited, but is preferably 10 to 1,000 nm, more preferably 10 to 120 nm. It is particularly preferable to consider the thickness depending on the intended use of the inspection composition. For example, when the inspection composition is to be used for pattern formation by EUV exposure or EB exposure, the thickness of the coating film is more preferably 10 to 100 nm, more preferably 15 to 70 nm. Furthermore, for example, when the inspection composition is to be used for pattern formation by ArF immersion exposure, the thickness of the coating film is more preferably 10 to 120 nm, more preferably 15 to 90 nm.

[0031] <Process X2> Step X2 is a step of removing the coating film formed in step X1 from the substrate using an alkaline developer (removal solvent). However, in step X2, the coating film is removed from the substrate without exposing the resist composition to actinic rays or radiation (i.e., without causing deterioration of the components in the coating film due to exposure). The phrase "without exposing the resist composition to actinic rays or radiation" means that the resist composition is not exposed to an exposure dose equal to or greater than the minimum exposure dose at which a residual film is observed. The various materials used in step X2 and the procedure for step X2 will be described below.

[0032] (Alkaline developer (removal solvent)) In step X2, an alkaline developer is used as the removal solvent. A typical example of the alkaline developer is an aqueous alkaline solution. The alkaline developer used in step X2 is not particularly limited as long as it can remove the coating film formed in step X1 from the substrate. Among these, it is preferable to use an alkaline developer that is used as a developer when forming a pattern using a resist composition containing an alkali-soluble component, which is the test composition.

[0033] The alkali source for the alkaline developer is not particularly limited, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, and dibutyldipentylammonium hydroxide, as well as quaternary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, and dimethylbis(2-hydroxyethyl)ammonium hydroxide; and cyclic amines such as pyrrole and piperidine. Of these, the alkali source is preferably a quaternary ammonium salt, more preferably a tetraalkylammonium hydroxide (the number of carbon atoms in the alkyl portion is preferably 1 to 6), and even more preferably tetramethylammonium hydroxide.

[0034] The content of the alkali source in the alkaline aqueous solution is, for example, preferably 0.1 to 20 mass %, more preferably 0.1 to 5.0 mass %, and even more preferably 2.0 to 3.0 mass %, relative to the total mass of the alkaline aqueous solution. The pH of the alkaline aqueous solution is, for example, preferably 10.0 to 15.0, more preferably 11.0 to 15.0, and even more preferably 12.0 to 15.0. The alkaline aqueous solution may contain alcohols and / or surfactants.

[0035] As the alkaline developer, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is particularly preferred.

[0036] In terms of further improving inspection accuracy, the removal solvent used in process X2 is used when the number of defects when the following defect inspection R1 is performed is 1.50 / cm 2 In other words, in order to further improve the accuracy of the defect inspection, the removal solvent used in step X2 is preferably one that has a defect count of 1.50 / cm or less when the following defect inspection R1 is carried out. 2 The removal solvent used in step X2 is preferably one that can detect defects of 0.75 / cm when the following defect inspection R1 is carried out, in order to further improve inspection accuracy. 2 More preferably, it is 0.15 pieces / cm or less. 2 It is more preferable that the density is equal to or less than 0.00 particles / cm. 2 That's all.

[0037] In terms of further improving inspection accuracy, the removal solvent used in process X2 is used when the number of defects of 20 nm or more in size is 1.50 / cm when the following defect inspection R1 is performed. 2 In other words, in order to further improve the accuracy of the defect inspection, the removal solvent used in step X2 is preferably such that the number of defects having a size of 20 nm or more calculated by the defect inspection R1 described below is 1.50 / cm. 2The removal solvent used in step X2 is preferably one that, when the following defect inspection R1 is carried out, detects defects of 20 nm or more at a rate of 0.75 / cm, in order to further improve inspection accuracy. 2 More preferably, it is 0.15 pieces / cm or less. 2 It is more preferable that the density is equal to or less than 0.00 particles / cm. 2 That's all. <Defect inspection R1> The defect inspection R1 includes the following steps ZA1 to ZA4. Process ZA1: A process of measuring the number of defects on the substrate using a defect inspection device Step ZA2: Applying a removal solvent to the substrate Step ZA3: A step of measuring the number of defects on the substrate to which the removal solvent has been applied using a defect inspection device. Step ZA4: A step of calculating the number of defects caused by the removal solvent by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3.

[0038] The substrate defects in the steps ZA1 and ZA3 can be measured using a defect inspection device (for example, a dark-field defect inspection device SP5 manufactured by KLA Tencor Corporation).

[0039] The defect inspection R1 will be described below. ·Process ZA1 Step ZA1 is a step of measuring the number of defects on the substrate using a defect inspection device. Specifically, the number of defects (preferably the number of defects with a size of 20 nm or more) present on the substrate is measured. The substrate used in step ZA1 is not particularly limited, but examples include substrates used in the manufacture of integrated circuit devices, and silicon wafers are preferred. The substrate defect inspection in the process ZA1 can be performed using a defect inspection device (for example, a dark field defect inspection device SP5 manufactured by KLA Tencor Corporation). By carrying out the above-mentioned step ZA1, the number of defects (preferably the number of defects having a size of 20 nm or more) (number of defects in the original substrate) that exist on the substrate before applying the step ZA2 is measured.

[0040] ·Process ZA2: Step ZA2 is a step of applying a removal solvent to the substrate. The method for applying the removal solvent to the substrate is not particularly limited, but spin coating using a spinner is preferred. The rotation speed when spin coating using a spinner is preferably 500 to 3000 rpm. The supply flow rate of the removal solvent is preferably 0.2 to 15 mL / s, and more preferably 0.2 to 12 mL / s. The supply time is preferably 3 to 300 seconds, more preferably 5 to 150 seconds, and even more preferably 5 to 120 seconds. After the removal solvent is applied to the substrate, the substrate is preferably dried. An example of a drying method is a method of drying by heating. Heating can be performed using a means provided in a normal exposure machine and / or developing machine, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 250°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, even more preferably 30 to 600 seconds, and particularly preferably 30 to 200 seconds. In one embodiment, heating is preferably performed at 100°C for 60 seconds.

[0041] ·Process ZA3 Step ZA3 is a step of measuring the number of defects on the substrate coated with the removal solvent using a defect inspection device. Specifically, the number of defects (preferably, the number of defects with a size of 20 nm or more) present on the substrate is measured. The substrate defect inspection in the process ZA3 can be performed using a defect inspection device (for example, a dark field defect inspection device SP5 manufactured by KLA Tencor Corporation). By carrying out the above step ZA3, the number of defects (preferably the number of defects having a size of 20 nm or more) present on the substrate after application of the removal solvent (number of defects after application of the removal solvent) is measured.

[0042] ·Process Z4 Process ZA4 is a process for calculating the number of defects caused by the removal solvent (number of removal solvent defects) by subtracting the number of defects measured in process ZA1 (number of defects on the original substrate) from the number of defects measured in process ZA3 (number of defects after application of the removal solvent). As described above, the number of defects obtained by carrying out the above step ZA4 is 1.50 / cm 2 Preferably, it is 0.75 pieces / cm or less. 2 More preferably, it is 0.15 pieces / cm or less. 2 The lower limit is, for example, 0.00 particles / cm. 2 That's all. As described above, the number of defects having a size of 20 nm or more obtained by carrying out the above step ZA4 is 1.50 / cm 2 Preferably, it is 0.75 pieces / cm or less. 2 More preferably, it is 0.15 pieces / cm or less. 2 The lower limit is, for example, 0.00 particles / cm. 2 That's all. If the number of defects resulting from the removal solvent used in step X2 is large, scattering may occur during the defect inspection of the substrate performed in step X3, hindering accurate measurement of the number of defects. For this reason, it is preferable to use a removal solvent with high cleanliness for the step X2, in order to improve the accuracy of the defect inspection in step X3 (and ultimately to improve the inspection accuracy of this inspection method).

[0043] (Step X2 procedure) There are no particular limitations on the method for removing the coating film formed in step X1 from the substrate using a removal solvent. Examples of removal methods include immersing the substrate in a tank filled with the removal solvent for a certain period of time, piling up the removal solvent on the substrate surface by surface tension and leaving it to stand for a certain period of time to remove it, spraying the removal solvent onto the substrate surface, and continuously discharging the removal solvent while scanning a removal solvent discharge nozzle at a constant speed onto a substrate that is rotating at a constant speed. Removal by the above methods can be carried out in an alkaline development unit. Other examples of the removal method include a removal method using a coater cup and a removal method using an alkali developing unit. A removal method using a spin coating method using a spinner is also preferred. The rotation speed when carrying out a removal method using a spin coating method using a spinner is preferably 500 to 3,000 rpm. The supply flow rate of the removal solvent is preferably 0.2 to 15 mL / s, more preferably 0.2 to 12 mL / s. The supply time is preferably 3 to 300 seconds, more preferably 5 to 180 seconds.

[0044] The temperature of the removing solvent is not particularly limited, but is preferably 20 to 160°C, more preferably 70 to 120°C. The removal time for the removal treatment using a removal solvent is, for example, 800 seconds or less, preferably 300 seconds or less, and more preferably 180 seconds or less, in terms of better inspection accuracy. The lower limit is, for example, 5 seconds or more. If the removal time in step X2 is too long, not only the coating but also minute components (foreign matter) are likely to be removed from the substrate, which may prevent accurate measurement of the number of defects in the defect inspection in step X3. Therefore, a shorter removal time used in step X1 is preferable in terms of better defect inspection accuracy in step X3 (and thus, in terms of further improving the inspection accuracy of this inspection method).

[0045] After the removal process is performed, the substrate is preferably dried. An example of a drying method is a method of drying by heating. Heating can be performed using a means provided in a normal exposure machine and / or developing machine, or may be performed using a hot plate or the like. The heating temperature is preferably 40 to 200°C, more preferably 70 to 160°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, even more preferably 30 to 600 seconds, and particularly preferably 30 to 200 seconds. In one embodiment, heating is preferably performed at 100°C for 60 seconds.

[0046] <Process X3> Step X3 is a step of measuring the number of defects on the substrate after the coating film has been removed in step X2 using a defect inspection device. Specifically, the number of defects present on the substrate (preferably, the number of defects having a size of 20 nm or more) is measured. The substrate defect inspection in step X3 can be performed using a defect inspection device (for example, a dark field defect inspection device SP5 manufactured by KLA Tencor Corporation). By carrying out the above step X3, the number of defects (preferably the number of defects having a size of 20 nm or more (total number of defects after solvent removal treatment)) present on the substrate after removal with the removal solvent is measured.

[0047] [Second embodiment of inspection method] A second embodiment of the inspection method will be described below. The second embodiment of the inspection method is a method for inspecting a resist composition (inspection composition) containing an alkali-soluble component, and includes steps X1, X2, and X3 (steps X3A and X3B), and, if necessary, step Y1. Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (removal solvent) without performing exposure treatment by irradiation with actinic rays or radiation. Step X3: Step X3 includes Step X3A and Step X3B. Step X3A: A step of measuring the number of defects on the substrate after removing the coating film (i.e., after undergoing step X2) using a defect inspection device. Step X3B: A step of calculating the number of defects originating from the inspection composition by subtracting the number of defects that existed on the substrate before applying step X1 (number of defects originating from the substrate: number of defects on the original substrate) from the number of defects measured in step X3A. However, if the number of defects originating from the substrate (number of defects on the original substrate) is unknown, the second embodiment of the inspection method further includes step Y1, in which the number of defects measured in step Y1 is taken as the number of defects originating from the substrate (number of defects on the original substrate). Process Y1: A process before process X1 in which the number of defects on the substrate to be used in process X1 is measured using a defect inspection device.

[0048] The second embodiment of the inspection method includes a step X3B in which the number of defects caused by the substrate (the number of defects on the original substrate) is subtracted from the number of defects measured in the step X3A (the total number of defects after the solvent removal treatment). This configuration allows the number of defects caused by the inspection composition to be inspected with higher accuracy.

[0049] Each step will be explained below. <Process X1 and Process X2> In the second embodiment of the inspection method, steps X1 and X2 are the same as steps X1 and X2 in the first embodiment of the inspection method described above.

[0050] <Process X3 (Process X3A and Process X3B)> Step X3 includes steps X3A and X3B. (Process X3A) In the second embodiment of the inspection method, step X3A is the same as step X3 in the first embodiment of the inspection method described above. (Process X3B) Step X3B is a step of calculating the number of defects originating from the test composition by subtracting the number of defects present on the substrate before applying step X1 (number of defects originating from the substrate: number of defects on the original substrate) from the number of defects measured in step X3A. If the number of defects originating from the substrate (number of defects on the original substrate) is already known from a catalog or the like, such a nominal value can be used. If the number of defects originating from the substrate is unknown, the second embodiment of the inspection method further includes step Y1, and the value measured in step Y1 is used as the number of defects originating from the substrate (number of defects on the original substrate).

[0051] <Process Y1> Step Y1 is a step performed before step X1 in which the number of defects on the substrate to be used in step X1 is measured using a defect inspection device. The process Y corresponds to the process of carrying out the method for measuring the number of defects in the original substrate, which was explained in the process X1 of the first embodiment of the inspection method, and the preferred aspects thereof are also the same.

[0052] [Third embodiment of inspection method] The third embodiment of the inspection method will be described below. The third embodiment of the inspection method is a method for inspecting a resist composition (inspection composition) containing an alkali-soluble component, and includes steps X1, X2, and X3 (steps X3A and X3C), and, if necessary, step ZX. Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (removal solvent) without performing exposure treatment by irradiation with actinic rays or radiation. Step X3: Step X3 includes Step X3A and Step X3C. Step X3A: A step of measuring the number of defects on the substrate after removing the coating film (i.e., after undergoing step X2) using a defect inspection device. Step X3C: A step of calculating the number of defects resulting from the inspection composition by subtracting the number of defects resulting from the removal solvent (number of removal solvent defects) from the number of defects measured in Step X3A. However, if the number of defects resulting from the removal solvent (number of removal solvent defects) is unknown, the third embodiment of the inspection method further includes Step ZX, in which the number of defects measured in Step ZX is set as the number of defects resulting from the removal solvent (number of removal solvent defects). Step ZX: A step of carrying out the following steps Z1 to Z4 before the step X2 (steps Z1 to Z4 are carried out in the order of step Z3, step Z1, step Z2, and step Z4). Step Z1: A step of applying the removal solvent used in step X2 to the substrate. Step Z2: A step of measuring the number of defects on the substrate to which the removal solvent has been applied using a defect inspection device. Process Z3: A process of measuring the number of defects on the substrate used in process Z1 using a defect inspection device. Step Z4: A step of calculating the number of defects resulting from the removal solvent used in step Z2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2.

[0053] The third embodiment of the inspection method includes a step X3C in which the number of defects caused by the removal solvent (the number of removal solvent defects) is subtracted from the number of defects measured in step X3A (the total number of defects after the solvent removal process). This configuration allows the number of defects caused by the inspection composition to be inspected with higher accuracy.

[0054] Each step will be explained below. <Process X1 and Process X2> In the third embodiment of the inspection method, steps X1 and X2 are the same as steps X1 and X2 in the first embodiment of the inspection method described above.

[0055] <Process X3 (Process X3A and Process X3C)> Step X3 includes Step X3A and Step X3C. (Process X3A) In the third embodiment of the inspection method, step X3A is the same as step X3 in the first embodiment of the inspection method described above. (Process X3C) Step X3C is a step of calculating the number of defects resulting from the test composition by subtracting the number of defects resulting from the removal solvent (number of removal solvent defects) from the number of defects measured in step X3A. If the number of defects caused by the removal solvent (number of removal solvent defects) is already known from a catalog or the like, such a nominal value can be used. If the number of defects caused by the removal solvent (number of removal solvent defects) is unknown, the third embodiment of the inspection method further includes step ZX, and the value measured in step ZX is used as the number of defects caused by the removal solvent (number of removal solvent defects).

[0056] <Process ZX (Process Z1~Process Z4)> Step ZX is a step, prior to step X2, of determining the number of defects resulting from the removal solvent used in step X2 (number of removal solvent defects). In process ZX, process Z1, process Z2, process Z3, and process Z4 correspond to process ZA2, process ZA3, process ZA1, and process ZA4, respectively, in defect inspection R1 described in process X2 of the first embodiment of the inspection method, and the preferred aspects thereof are also the same.

[0057] [Fourth embodiment of inspection method] The fourth embodiment of the inspection method will be described below. The fourth embodiment of the inspection method is a method for inspecting a resist composition (inspection composition) containing an alkali-soluble component, and includes steps X1, X2, and X3 (steps X3A and X3D), and, as necessary, steps Y1 and ZX. Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (removal solvent) without performing exposure treatment by irradiation with actinic rays or radiation. Step X3: Step X3 includes Step X3A and Step X3D. Step X3A: A step of measuring the number of defects on the substrate after removing the coating film (i.e., after undergoing step X2) using a defect inspection device. Step X3D: A step of calculating the number of defects resulting from the inspection composition (number of composition defects) by subtracting the number of defects present on the substrate before applying step X1 (number of defects resulting from the substrate: number of defects on the original substrate) and the number of defects resulting from the removal solvent (number of removal solvent defects) from the number of defects measured in step X3A. However, if the number of defects resulting from the substrate (number of defects on the original substrate) is unknown, the fourth embodiment of the inspection method further includes step Y1, and the number of defects measured in this step Y1 is taken as the number of defects resulting from the substrate (number of defects on the original substrate). Furthermore, if the number of defects resulting from the removal solvent (number of removal solvent defects) is unknown, the fourth embodiment of the inspection method further includes step ZX, and the number of defects measured in this step ZX is taken as the number of defects resulting from the removal solvent (number of removal solvent defects). Step Y1: Before the step X1, a step of measuring the number of defects on the substrate to be used in the step X1 using a defect inspection device. Step ZX: A step including steps Z1 to Z4, which is carried out before step X2 (steps Z1 to Z4 are carried out in the order of step Z3, step Z1, step Z2, and step Z4). Step Z1: A step of applying the removal solvent used in step X2 to the substrate. Step Z2: A step of measuring the number of defects on the substrate to which the removal solvent has been applied using a defect inspection device. Process Z3: A process of measuring the number of defects on the substrate used in process Z1 using a defect inspection device. Step Z4: A step of calculating the number of defects resulting from the removal solvent used in step Z2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2.

[0058] The fourth embodiment of the inspection method includes a step X3D in which the number of defects caused by the substrate (the number of original substrate defects) and the number of defects caused by the removal solvent (the number of removal solvent defects) are subtracted from the number of defects measured in step X3A (the total number of defects after the solvent removal process). This configuration allows the number of defects caused by the inspection composition (the number of composition defects) to be inspected with higher accuracy.

[0059] Each step will be explained below. <Process X1 and Process X2> In the fourth embodiment of the inspection method, steps X1 and X2 are the same as steps X1 and X2 in the first embodiment of the inspection method described above.

[0060] <Process X3 (Process X3A and Process X3D)> Step X3 includes steps X3A and X3D. (Process X3A) In the fourth embodiment of the inspection method, step X3A is the same as step X3 in the first embodiment of the inspection method described above. (Process X3D) Step X3B is a step of calculating the number of defects resulting from the test composition (number of composition defects) by subtracting the number of defects that existed on the substrate before applying step X1 (number of defects resulting from the substrate: number of defects on the original substrate) and the number of defects resulting from the removal solvent (number of removal solvent defects) from the number of defects measured in step X3A. If the number of defects originating from the substrate (number of defects on the original substrate) is already known from a catalog or the like, such a nominal value can be used. If the number of defects originating from the substrate is unknown, the fourth embodiment of the inspection method further includes step Y1, and the value measured in step Y1 is used as the number of defects originating from the substrate (number of defects on the original substrate). Furthermore, if the number of defects resulting from the removal solvent (number of removal solvent defects) is already known from a catalog or the like, such a nominal value can be used. If the number of defects resulting from the removal solvent (number of removal solvent defects) is unknown, the fourth embodiment of the inspection method further includes step ZX, and the value measured in this step ZX is used as the number of defects resulting from the removal solvent (number of removal solvent defects).

[0061] <Process Y1> In the fourth embodiment of the inspection method, step Y1 is the same as step Y1 in the second embodiment of the inspection method described above.

[0062] <Process ZX> In the fourth embodiment of the inspection method, the step ZX is the same as the step ZX in the third embodiment of the inspection method described above.

[0063] [Fifth embodiment of inspection method] The fifth embodiment of the inspection method is a method for inspecting a resist composition (inspection composition) containing an alkali-soluble component, and includes the following steps X1, X2, X3 (steps X3A and X3E), Y1, and ZX. Step X1: A step of applying the test composition to a substrate to form a coating film Step X2: A step of removing the coating film from the substrate using an alkaline developer (removal solvent) without performing exposure treatment by irradiation with actinic rays or radiation. Step X3A: A step of measuring the number of defects on the substrate after removing the coating film using a defect inspection device. Process Y1: A process prior to the process X1 in which the number of defects on the substrate to be used in the process X1 is measured using a defect inspection device. Step ZX: A step including steps Z1 to Z4, which is carried out before the step X2 (steps Z1 to Z4 are carried out in the order of step Z3, step Z1, step Z2, and step Z4). Step Z1: A step of applying the removal solvent used in step X2 to the substrate. Step Z2: A step of measuring the number of defects on the substrate to which the removal solvent has been applied using a defect inspection device. Process Z3: A process of measuring the number of defects on the substrate used in process Z1 using a defect inspection device. Step Z4: A step of calculating the number of defects resulting from the removal solvent used in step Z2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2. Step 3E: A step of calculating the number of defects caused by the test composition by subtracting the number of defects calculated in step Y1 and the number of defects calculated in step Z4 from the number of defects measured in step X3A.

[0064] Each step will be explained below.

[0065] <Process X1 and Process X2> In the fourth embodiment of the inspection method, steps X1 and X2 are the same as steps X1 and X2 in the first embodiment of the inspection method described above.

[0066] <Process X3 (Process X3A and Process X3E)> Step X3 includes steps X3A and X3E. (Process X3A) In the fifth embodiment of the inspection method, step X3A is the same as step X3 in the first embodiment of the inspection method described above. (Process X3E) Step 3E is a step of calculating the number of defects resulting from the test composition (number of composition defects) by subtracting the number of defects calculated in step Y1 (number of original substrate defects) and the number of defects calculated in step Z4 (number of removed solvent defects) from the number of defects measured in step X3A (total number of defects after solvent removal treatment).

[0067] <Process Y1> In the fifth embodiment of the inspection method, step Y1 is the same as step Y1 in the second embodiment of the inspection method described above.

[0068] <Process ZX> In the fifth embodiment of the inspection method, the step ZX is the same as the step ZX in the third embodiment of the inspection method described above.

[0069] Test Composition The inspection composition in the inspection method of the present invention is a resist composition containing an alkali-soluble component. An example of an embodiment of a resist composition containing an alkali-soluble component suitable as the inspection composition will be described below.

[0070] <<Resist composition containing an alkali-soluble component>> A resist composition containing an alkali-soluble component refers to a resist composition in which the exposed areas are hardened and the unexposed areas can be removed with an alkali developer. The resist composition containing an alkali-soluble component can be, for example, a known alkaline-developable negative resist composition. In alkaline-developable negative resist compositions, the exposed areas typically harden, while the unexposed areas can be removed with an alkaline developer. The alkali-soluble component is preferably a component that can be dissolved (either partially or completely) in an alkali developer used in pattern formation. A preferred embodiment of the alkali-soluble component is an alkali-soluble resin having a phenolic hydroxyl group. The phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxyl group. The aromatic ring of the aromatic ring group may be either monocyclic or polycyclic, and examples thereof include a benzene ring and a naphthalene ring. An example of an embodiment of a negative resist composition suitable as an inspection composition will be described below.

[0071] <Preferred embodiment 1 of negative resist composition> Examples of alkali-developable negative resist compositions include compositions containing an alkali-soluble resin, a photoacid generator, a crosslinking agent, and a solvent.

[0072] A specific embodiment of the first preferred embodiment of the negative resist composition will be explained below using the negative resist composition (R) as an example.

[0073] (Negative resist composition (R)) The negative resist composition (R) contains an alkali-soluble resin, a photoacid generator, a crosslinking agent, and a solvent.

[0074] <Alkali-soluble resin> The alkali-soluble resin is preferably an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as "resin (P)"). The definition of "phenolic hydroxyl group" is as described above.

[0075] Repeating units containing phenolic hydroxyl groups The resin (P) more preferably contains a repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is preferably, for example, a repeating unit represented by the following general formula (II).

[0076] [ka]

[0077] In the formula, R2 represents a hydrogen atom, a methyl group which may have a substituent, or a halogen atom (preferably a fluorine atom). B' represents a single bond or a divalent linking group. Ar' represents an aromatic ring group. m represents an integer of 1 or greater.

[0078] Examples of the methyl group represented by R2 which may have a substituent include a trifluoromethyl group and a hydroxymethyl group. R2 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0079] The divalent linking group represented by B' is preferably a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms), a sulfonyl group (-S(=O)2-), -O-, -NH-, or a divalent linking group formed by combining these. Among these, B' is preferably a single bond, a carbonyloxy group (-C(=O)-O-), or -C(=O)-NH-, more preferably a single bond or a carbonyloxy group (-C(=O)-O-), and most preferably a single bond.

[0080] The aromatic ring represented by Ar' may be either a monocyclic or polycyclic aromatic ring, and examples thereof include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, which may have a substituent; and aromatic heterocycles containing heterocycles, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. Among these, aromatic hydrocarbon rings are preferred, with a benzene ring or a naphthalene ring being more preferred, and a benzene ring being even more preferred. The aromatic ring represented by Ar' may further have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, and an arylcarbonyl group.

[0081] m is preferably an integer of 1 to 5, more preferably 1 to 3, and even more preferably 1. When m is 1 and Ar' is a benzene ring, the substitution position of -OH may be any of the para-position, meta-position, and ortho-position relative to the bonding position of the benzene ring to B' (or the polymer main chain when B' is a single bond), and the para-position is preferred.

[0082] The resin (P) may be a homopolymer composed only of the repeating units having the above-mentioned phenolic hydroxyl group, or may contain other repeating units. When the resin (P) is a copolymer, the content of repeating units having a phenolic hydroxyl group is preferably 10 to 98 mol %, more preferably 30 to 97 mol %, and even more preferably 40 to 95 mol %, based on all repeating units in the resin (P).

[0083] Repeating units containing a group with an acid-non-decomposable hydrocarbon structure The resin (P) also preferably contains a repeating unit containing a group having an acid-non-decomposable hydrocarbon structure (hereinafter also referred to as "acid-non-decomposable repeating unit"). The term "non-acid-decomposable group" means a group that does not undergo a decomposition reaction due to the acid generated by the photoacid generator. The group having a hydrocarbon structure is intended to be a group containing at least one of a linear or branched hydrocarbon group and a cyclic (monocyclic or polycyclic) alicyclic hydrocarbon group, and may be bridged. In addition, at least a portion of the carbon atoms of the alicyclic hydrocarbon group may be substituted with a heteroatom such as an oxygen atom and / or a carbonyl carbon (=CO). Among the groups having a hydrocarbon structure, cyclic (either monocyclic or polycyclic) alicyclic hydrocarbon groups are preferred.

[0084] Examples of the linear and branched hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms. The monocyclic alicyclic hydrocarbon group is preferably a cycloalkyl group having 3 to 8 carbon atoms. Examples of alicyclic hydrocarbons constituting polycyclic alicyclic hydrocarbon groups include alicyclic hydrocarbons having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. Among these, the alicyclic hydrocarbon is preferably a polycyclic cyclo ring having 6 to 30 carbon atoms, more preferably an adamantane ring, decalin ring, norbornane ring, norbornene ring, cedrol ring, isobornane ring, bornane ring, dicyclopentane ring, α-pinene ring, tricyclodecane ring, tetracyclododecane ring, or androstane ring, and even more preferably an adamantane ring.

[0085] The group having a hydrocarbon structure may further have a substituent, such as an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 6 carbon atoms), a carboxyl group, a carbonyl group, a thiocarbonyl group, an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), or a group formed by combining these groups (preferably having a total of 1 to 30 carbon atoms, more preferably having a total of 1 to 15 carbon atoms).

[0086] Among the repeating units containing a group having an acid-non-decomposable hydrocarbon structure, a repeating unit represented by the following general formula (1) is particularly preferred.

[0087] [ka]

[0088] In the formula, R represents a hydrogen atom or a methyl group, X represents a group having an acid-non-decomposable hydrocarbon structure, Ar represents an aromatic ring, and L represents a single bond or a divalent linking group.

[0089] R is preferably a hydrogen atom.

[0090] Examples of the divalent linking group represented by L include a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms), a sulfonyl group (-S(=O)2-), -O-, -NH-, and divalent linking groups formed by combining these. L is preferably a single bond.

[0091] Examples of the aromatic ring represented by Ar include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, which may have a substituent; and aromatic heterocycles, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. The aromatic ring represented by Ar is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. The aromatic ring represented by Ar may further have a substituent, such as an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 6 carbon atoms), a carboxyl group, or an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms).

[0092] The group having a non-acid-decomposable hydrocarbon group represented by X is preferably a group represented by -Y-X2 (wherein Y is a divalent linking group and X2 is a group having the above-mentioned hydrocarbon structure). Examples of the divalent linking group represented by Y include a carbonyl group, a thiocarbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms), a sulfonyl group, -COCH2-, -NH-, and a divalent linking group formed by combining these (preferably having a total of 1 to 20 carbon atoms, more preferably having a total of 1 to 10 carbon atoms), and a carbonyl group is preferred.

[0093] Examples of the group having a hydrocarbon structure represented by X2 include the groups having a hydrocarbon structure described above. Among these, the group having a hydrocarbon structure represented by X2 is preferably a cyclic (either monocyclic or polycyclic) alicyclic hydrocarbon group, and more preferably an adamantane group.

[0094] The content of repeating units containing a group having an acid-non-decomposable hydrocarbon structure is preferably 1 to 40 mol %, more preferably 2 to 30 mol %, based on the total repeating units of the resin (P).

[0095] Other repeating units The resin (P) may contain other repeating units. Examples of other repeating units include the repeating units disclosed in paragraphs 0125 to 0237 of JP-A-2015-148688.

[0096] The weight average molecular weight (Mw) of the resin (P) is preferably from 1,000 to 200,000, more preferably from 2,000 to 30,000, and even more preferably from 3,000 to 25,000. The dispersity (Mw / Mn) is usually from 1.0 to 3.0, preferably from 1.0 to 2.6, more preferably from 1.0 to 2.0, and even more preferably from 1.1 to 2.0.

[0097] The resin (P) may be used alone or in combination of two or more kinds. The content of the resin (P) in the composition is preferably 20 to 99.5% by mass, more preferably 40 to 99% by mass, and even more preferably 55 to 98% by mass, based on the total solid content.

[0098] <Crosslinking agent> The crosslinking agent is a compound (including resins) having a crosslinkable group capable of crosslinking a resin, and is preferably a compound that crosslinks the resin (P) by the action of an acid. As the crosslinking agent, known compounds can be used appropriately, and examples thereof include the known compounds disclosed in paragraphs

[0379] to

[0431] of the specification of U.S. Patent Application Publication No. 2016 / 0147154A1 and paragraphs

[0064] to

[0141] of the specification of U.S. Patent Application Publication No. 2016 / 0282720A1. Examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring, with a hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring being preferred. The crosslinking agent is preferably a compound having two or more crosslinkable groups. The crosslinking agent is preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea-based compound (a compound having a urea structure), or a melamine-based compound (a compound having a melamine structure). The crosslinking agent may be used alone or in combination of two or more kinds. The content of the crosslinking agent in the composition is preferably from 1 to 50% by mass, more preferably from 3 to 40% by mass, and further preferably from 5 to 30% by mass, based on the total solid content of the composition.

[0099] <Photoacid generator> A photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation. The photoacid generator includes a photoacid generator X and a photoacid generator Y. The composition may contain only the photoacid generator X, or may contain both the photoacid generator X and the photoacid generator Y.

[0100] Photoacid generator X The photoacid generator X is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation, such as a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound.

[0101] Known compounds that generate an acid upon irradiation with actinic rays or radiation can be appropriately selected and used alone or in mixtures as the photoacid generator X. For example, known compounds disclosed in paragraphs

[0125] to

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

[0086] to

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

[0323] to

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

[0102] As the photoacid generator X, for example, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferred.

[0103] [ka]

[0104] In the above general formula (ZI), R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The organic group as the aryl group generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms. Also, R 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these include alkylene groups (for example, butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-. Z - represents an anion (preferably a non-nucleophilic anion).

[0105] Next, general formulae (ZII) and (ZIII) will be explained. In general formulas (ZII) and (ZIII), R 204~R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 ~R 207 The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 ~R 207 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

[0106] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 ~R 207 Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Z - represents an anion.

[0107] Z in general formula (ZI) - and Z in general formula (ZII) - The anion is preferably an anion represented by the following general formula (3).

[0108] [ka]

[0109] In the general formula (3), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0110] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. Furthermore, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and particularly preferably both Xf are fluorine atoms.

[0111] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R4s and R5s are present, they may be the same or different. The alkyl group represented by R4 and R5 may have a substituent and preferably has a carbon number of 1 to 4. R4 and R5 are preferably hydrogen atoms. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in general formula (3).

[0112] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, and -NHCO-alkylene group- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, and -OCO-alkylene group- are more preferred.

[0113] W represents an organic group containing a cyclic structure, and among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0114] The aryl group may be monocyclic or polycyclic and includes, for example, phenyl, naphthyl, phenanthryl, and anthryl. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups can better suppress acid diffusion. The heterocyclic group may or may not have aromaticity. Examples of aromatic heterocycles include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of non-aromatic heterocycles include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of lactone rings and sultone rings include the lactone structures and sultone structures exemplified for the resins described above. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

[0115] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to ring formation) may be a carbonyl carbon.

[0116] The anion represented by general formula (3) is SO3 - -CF2-CH2-OCO-(L)q'-W, SO3 - -CF2-CHF-CH2-OCO-(L)q'-W, SO3 - -CF2-COO-(L)q'-W, SO3 - -CF2-CF2-CH2-CH2-(L)qW, SO3 - -CF2-CH(CF3)-OCO-(L)q'-W is preferred, where L, q and W are the same as in general formula (3), and q' represents an integer of 0 to 10.

[0117] Z in general formula (ZI)- and Z in general formula (ZII) - may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0118] Examples of the photoacid generator X include the photoacid generators disclosed in paragraphs

[0135] to

[0171] of WO 2018 / 193954, paragraphs

[0077] to

[0116] of WO 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of WO 2017 / 154345, the contents of which are incorporated herein by reference.

[0119] The photoacid generator X may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Alternatively, the photoacid generator X may be in the form of a low molecular weight compound and a form of being incorporated into a part of a polymer in combination. The photoacid generator X is preferably in the form of a low molecular weight compound. When the photoacid generator X is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. When the photoacid generator X is in a form in which it is incorporated into a part of a polymer, it may be incorporated into a part of the above-mentioned resin (P), or may be incorporated into a resin different from the resin (P). The photoacid generator X may be used alone or in combination of two or more kinds.

[0120] The content of the photoacid generator X in the composition (the total content if multiple types are present) is preferably 0.1 to 35 mass%, more preferably 0.5 to 25 mass%, even more preferably 1 to 20 mass%, and particularly preferably 1 to 15 mass%, based on the total solid content of the composition.

[0121] Photoacid generator Y The photoacid generator Y is a photoacid generator having an onium salt structure that is weaker in acidity than the photoacid generator X. When a photoacid generator X is mixed with an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator X, the acid generated by the photoacid generator X upon irradiation with actinic rays or radiation collides with an unreacted onium salt having a weak acid anion, releasing the weak acid through salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with lower catalytic activity, and the acid appears to be deactivated, making it possible to control acid diffusion.

[0122] The photoacid generator Y is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

[0123] [ka]

[0124] In the formula, R 51 is a hydrocarbon group which may have a substituent, and Z 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon adjacent to S is not substituted with a fluorine atom), and R 52 is an organic group, and Y 3 is a linear, branched or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing a fluorine atom, M + are each independently an ammonium cation, a sulfonium cation, or an iodonium cation.

[0125] M + Preferred examples of the sulfonium cation or iodonium cation represented by the following general formula (ZI) and the iodonium cation represented by the following general formula (ZII) are mentioned.

[0126] The onium salt (DC) that is a weak acid relative to the photoacid generator may be a compound (hereinafter also referred to as "compound (DCA)") that has a cationic moiety and an anionic moiety in the same molecule, and the cationic moiety and the anionic moiety are linked by a covalent bond. The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

[0127] [ka]

[0128] In the general formulae (C-1) to (C-3), R1, R2, and R3 each independently represent a substituent having one or more carbon atoms. L1 represents a divalent linking group or a single bond that links the cationic moiety and the anionic moiety. -X - -COO - , -SO3 - , -SO2 - , and -N - represents an anionic moiety selected from -R4, where R4 represents a monovalent substituent having at least one of a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)-), and a sulfinyl group (-S(=O)-) at the bonding site with the adjacent N atom. R1, R2, R3, R4, and L1 may be bonded to each other to form a ring structure. In addition, in general formula (C-3), two of R1 to R3 may be combined to represent one divalent substituent, which may be bonded to the N atom via a double bond.

[0129] Examples of the substituent having one or more carbon atoms in R1 to R3 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group, etc. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

[0130] Examples of L1 as a divalent linking group include a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a group formed by combining two or more of these. L1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0131] The content of the photoacid generator Y in the composition (the total content when multiple types are present) is 1.0 × 10 based on the total solid content of the composition. -4 It is preferably 1.0×10 mass% or less. -5 It is more preferable that the content is % by mass or less.

[0132] <Basic compounds> The basic compound functions as an acid diffusion controller, specifically, it acts as a quencher that traps the acid generated from the photoacid generator or the like upon exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area caused by the excess acid generated. Examples of acid diffusion controllers that can be used include basic compounds (CA), basic compounds (CB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, low molecular weight compounds (CD) that have a nitrogen atom and a group that is cleaved by the action of an acid, and onium salt compounds (CE) that have a nitrogen atom in the cation moiety.

[0133] As the basic compound, a known acid diffusion controller can be appropriately used. For example, the known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller. Specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

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

[0137] to

[0155] of WO 2020 / 066824, specific examples of low molecular weight compounds (CD) having a nitrogen atom and a group that is released by the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824, and specific examples of onium salt compounds (CE) having a nitrogen atom in the cation moiety include those described in paragraph

[0164] of WO 2020 / 066824. The contents of these are incorporated herein by reference.

[0134] One embodiment of the basic compound is preferably compound (CE), more preferably a compound having a basic moiety containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferred that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferred that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom. Preferred specific examples of compound (CE) include, but are not limited to, the compounds disclosed in paragraph

[0203] of the specification of US Patent Application Publication No. 2015 / 0309408A1.

[0135] Preferred examples of the basic compound are shown below, but the present invention is not limited to these: Me represents a methyl group.

[0136] [ka]

[0137] The basic compounds may be used alone or in combination of two or more. The content of the basic compound in the composition (the total content when multiple types are present) is preferably from 0.001 to 20 mass %, more preferably from 0.01 to 10 mass %, based on the total solid content of the composition.

[0138] <Solvent> As the solvent, a known resist solvent can be appropriately used, for example, the known solvents disclosed in paragraphs

[0665] to

[0670] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0210] to

[0235] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0424] to

[0426] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0357] to

[0366] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used. Examples of solvents that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0139] As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure with a solvent having no hydroxyl group may be used. The solvent having a hydroxyl group and the solvent not having a hydroxyl group can be appropriately selected from the above-mentioned exemplified compounds, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, and more preferably propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate (EL). In addition, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate, etc. are preferred, among which propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate is more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone is even more preferred. As the solvent having no hydroxyl group, propylene carbonate is also preferred. The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent not having a hydroxyl group is 1 / 99 to 99 / 1, preferably 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50 mass % or more of the solvent not having a hydroxyl group is preferred in terms of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a solvent containing propylene glycol monomethyl ether acetate alone or a mixed solvent containing two or more kinds of propylene glycol monomethyl ether acetate.

[0140] <Other additives> In addition to the components described above, the composition of the present invention may appropriately contain surfactants, carboxylic acids, carboxylic acid onium salts, dissolution inhibiting compounds having a molecular weight of 3,000 or less as described in, for example, Proceedings of SPIE, 2724, 355 (1996), dyes, plasticizers, photosensitizers, light absorbers, antioxidants, and the like.

[0141] Carboxylic acids can also be suitably used to improve performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred. When the composition contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10 mass %, more preferably 0.01 to 5 mass %, and even more preferably 0.01 to 3 mass %, based on the total solid content of the composition.

[0142] As the surfactant, a fluorine-based and / or silicon-based surfactant is preferred. These surfactants may be used alone or in combination of two or more. When the composition contains a surfactant, the content thereof is preferably 0 to 2 mass %, more preferably 0.0001 to 2 mass %, and even more preferably 0.0005 to 1 mass %, based on the total solid content of the composition.

[0143] The solid content concentration of the composition is preferably from 1.0 to 10 mass %, more preferably from 2.0 to 5.7 mass %, and even more preferably from 2.0 to 5.3 mass %.

[0144] <Preferred embodiment 2 of negative resist composition> Another example of an alkali-developable negative resist composition is a composition containing a polymerizable compound, a photopolymerization initiator, and a solvent. In the composition, the polymerizable compound is preferably an alkali-soluble component. The composition also preferably contains a resin. The resin is preferably an alkali-soluble resin. The alkali-soluble resin can also be used as a dispersant or binder. When the composition contains an alkali-soluble resin, the content of the resin is preferably 0.1 to 40 mass % based on the total solid content of the composition. In addition, when the polymerizable compound contains a cyclic ether group, a methylol group, or an alkoxymethyl group, the composition preferably further contains a curing agent. The composition may also contain components such as a colorant (pigment or the like), a surfactant, a polymerization inhibitor, a silane coupling agent, an ultraviolet absorber, and an antioxidant.

[0145] Examples of the polymerizable compound include compounds having a polymerizable group (polymerizable compound). Examples of the polymerizable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, a methylol group, and an alkoxymethyl group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinylphenyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The polymerizable compound may be a monomer or a polymer. When the polymerizable compound is a monomer, the number of polymerizable groups in the molecule is not particularly limited as long as it is 1 or more, preferably 2 or more, and more preferably 3 or more. The upper limit is not particularly limited, but is preferably 15 or less, and more preferably 6 or less. When the polymerizable compound is a polymer, it is preferably a polymer containing a repeating unit having a polymerizable group.

[0146] When the polymerizable compound is a monomer, the molecular weight of the polymerizable compound is preferably less than 2,000, and more preferably not more than 1,500. The lower limit is preferably 100 or more, and more preferably 200 or more. When the polymerizable compound is a polymer, the weight-average molecular weight (Mw) of the polymerizable compound is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

[0147] The polymerizable compounds may be used alone or in combination of two or more. The content of the polymer compound is preferably 1 to 95% by mass of the total solid content of the composition.

[0148] The solvent may be water or an organic solvent. Examples of the organic solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. The solvents may be used alone or in combination of two or more. The content of the solvent in the composition is preferably 10 to 97% by mass.

[0149] The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light in the ultraviolet to visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0150] The photopolymerization initiators may be used alone or in combination of two or more. The content of the photopolymerization initiator is preferably 0.1 to 40% by mass of the total solid content of the composition.

[0151] When the composition contains a compound having a cyclic ether group, the composition preferably further contains a curing agent. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds. When a curing agent is used, the content of the curing agent is preferably 0.01 to 20 parts by mass per 100 parts by mass of the compound having a cyclic ether group.

[0152] Examples of the above-mentioned alkaline-developable negative resist composition include curable compositions that can be used to form various cured films in the manufacturing process of solid-state imaging devices (for example, curable compositions for producing light-shielding films or color filters). Examples of such curable compositions include those disclosed in JP-A-2020-126253 and JP-A-2020-073989.

[0153] [Method for producing actinic ray- or radiation-sensitive composition] The method for producing the actinic ray-sensitive or radiation-sensitive composition (resist composition) of the present invention comprises the following composition preparation step and inspection step. Composition preparation step: A step of preparing a resist composition (inspection composition) containing an alkali-soluble component. Inspection step: A step of inspecting the resist composition (inspection composition) containing the alkali-soluble component obtained in the composition preparation step based on the inspection method of the present invention. The preparation method and inspection method for the resist composition (inspection composition) containing an alkali-soluble component are as described above, and the preferred embodiments are also the same.

[0154] If the number of defects originating from the resist composition obtained through the composition preparation step is detected in the inspection step to be greater than a desired value, it is preferable to further subject the inspection composition that has been subjected to the inspection step to a purification treatment. Furthermore, the inspection step may be performed only once or multiple times after the preparation of the resist composition.

[0155] A preferred embodiment of the production method of the present invention includes the following composition preparation step, testing step, purification step, and retesting step. The above production method may further include a repeating step (the repeating step may be repeated one or more times) as necessary. Composition preparation step: A step of preparing a resist composition (inspection composition) containing an alkali-soluble component. Inspection step: A step of inspecting the resist composition (inspection composition) obtained in the composition preparation step based on the inspection method of the present invention. Purification step: A step of further purifying the resist composition that has undergone the defect inspection step (e.g., filtration). Re-inspection step: A step of re-inspecting the resist composition (inspection composition) that has undergone the purification step based on the inspection method of the present invention. Repeating step: if the number of defects caused by the resist composition detected in the re-inspection step does not satisfy a predetermined value, the refining step and the subsequent re-inspection step are carried out again.

[0156] [Electronic device manufacturing method] The present invention also relates to a method for manufacturing an electronic device, which includes a step of carrying out an inspection based on the above-described inspection method of the present invention, and to an electronic device manufactured by this manufacturing method. A specific embodiment of the method for producing an electronic device preferably includes steps based on the method for producing the composition of the present invention described above. There are no particular limitations on the electronic device, and it is suitable for incorporation into, for example, electrical and electronic equipment (such as home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment). [Example]

[0157] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0158] [Preparation of Resist Compositions of Examples and Comparative Examples] [Preparation of Resist Compositions A, A-1, and A-2: Negative Resist Compositions] A negative resist composition, resist composition A, was prepared according to the following procedure. Furthermore, resist composition A was subjected to the following two different purification treatments to prepare two resist compositions, A-1 and A-2.

[0159] <Preparation of Resist Composition A> 61.2 parts by weight of the following resin P-8 7.5 parts by weight of photoacid generator A-12 (listed below) 4.5 parts by mass of the following photoacid generator B-1: 0.3 parts by mass of the following basic compound Q-1 26.4 parts by mass of crosslinking agent X-1 (see below) Solvent (EL / PGME / PEGMEA (mass ratio: 60 / 20 / 20)) in an amount that results in a solids concentration of 2.3 mass%

[0160] (Resin P-8) [ka]

[0161] The numerical values ​​assigned to each repeating unit in Resin P-8 indicate molar ratios.

[0162] (Photoacid generator A-12) [ka]

[0163] (Photoacid generator B-1) [ka]

[0164] (Basic compound Q-1) [ka]

[0165] (Crosslinking agent X-1) [ka]

[0166] <Filtering resist solution> Furthermore, resist composition A prepared by the above procedure was subjected to the following two different purification treatments to prepare two types of resist compositions, resist compositions A-1 and A-2.

[0167] (Resist Composition A-1) 12,000 g of resist composition A was filtered through the following two-stage filters to obtain resist composition A-1. 1st stage: PALL nylon filter with pore size of 20 nm (filter C) Second stage: Entegris polyethylene filter with a pore size of 3 nm (filter D) (Resist Composition A-2) 12,000 g of resist composition A was filtered through the following two-stage filters to obtain resist composition A-2. 1st stage: PALL nylon filter with 5 nm pore size (Filter A) Second stage: Entegris polyethylene filter with a pore size of 1 nm (filter B)

[0168] [Preparation of Resist Compositions B, B-1, B-2A, and B-2B: Negative Resist Compositions] A negative resist composition, resist composition B, was prepared according to the following procedure. Furthermore, resist composition B was subjected to the three different purification treatments described below to prepare three types of resist compositions: resist compositions B-1, B-2A, and B-2B. Resist composition B-2B was purified in the same manner as resist composition B-2A, except that the filter was pre-washed immediately before the filtration process.

[0169] <Preparation of Resist Composition B> 57.7 parts by mass of the above resin P-8 8.1 parts by mass of the above photoacid generator A-12 5.0 parts by mass of the above photoacid generator B-1 1.0 part by mass of the basic compound Q-1 28.2 parts by mass of the above crosslinking agent X-1 Solvent (EL / PGME / PEGMEA (mass ratio: 60 / 20 / 20)) in an amount that results in a solids concentration of 2.6 mass%

[0170] <Filtering resist solution> Furthermore, resist composition B was subjected to the three different purification treatments described below to prepare three types of resist compositions: resist compositions B-1, B-2A, and B-2B.

[0171] (Resist Composition B-1) 12,000 g of resist composition B was filtered through the following two-stage filters to obtain resist composition B-1. 1st stage: PALL nylon filter with 5 nm pore size (Filter A) Second stage: Entegris polyethylene filter with a pore size of 1 nm (filter B)

[0172] (Resist composition B-2A) 12,000 g of resist composition B was subjected to circulation filtration 14 times through the following two-stage filter to obtain resist composition B-2A. (Note that 14 circulation filtrations was defined as the number of times that the flow rate was measured and 14 times the input amount of 12,000 g was passed through.) 1st stage: PALL nylon filter with 5 nm pore size (Filter A) Second stage: Entegris polyethylene filter with a pore size of 1 nm (filter B)

[0173] (Resist composition B-2B) 12,000 g of resist composition B was subjected to circulation filtration 14 times through the following two-stage filter to obtain resist composition B-2B. (Note that 14 circulation filtrations was defined as the number of times that the flow rate was measured and 14 times the input amount of 12,000 g was passed through.) However, immediately before carrying out the circulation filtration, the filter was pre-cleaned using the solvent used in preparing the resist composition by passing the solvent through the filter. 1st stage: PALL nylon filter with 5 nm pore size (Filter A) Second stage: Entegris polyethylene filter with a pore size of 1 nm (filter B)

[0174] [Preparation of Resist Compositions C and C-1 (Comparative Positive Resist Compositions)] A negative resist composition, resist composition C, was prepared according to the following procedure. Resist composition C was subjected to the following filtration treatment to prepare resist composition C-1.

[0175] <Preparation of Resist Composition C> 77.4 parts by mass of the following resin P-1 16.5 parts by mass of the following photoacid generator A-11: 5.1 parts by mass of the above photoacid generator B-1 1.0 part by mass of the basic compound Q-1 Solvent (EL / PGME / PEGMEA (mass ratio: 60 / 20 / 20)) in an amount that results in a solids concentration of 2.6 mass%

[0176] (Resin P-1) [ka]

[0177] The numerical values ​​assigned to each repeating unit in the resin P-1 indicate molar ratios.

[0178] (Photoacid Generator A-11) [ka]

[0179] <Filtering resist solution> Resist composition C prepared by the above procedure was subjected to the purification treatment described below to prepare resist composition C-1.

[0180] (Resist Composition C-1) 12,000 g of resist composition B was filtered through the following two-stage filters to obtain resist composition C-1. 1st stage: PALL nylon filter with 5 nm pore size (Filter A) Second stage: Entegris polyethylene filter with a pore size of 1 nm (filter B)

[0181] [Preparing alkaline developer (removal solvent used in step X2)] [Types of alkaline developers (removal solvents)] <Types of alkaline developers> As the alkaline developers, the following alkaline developers X and Y were prepared. Furthermore, alkaline developer X was subjected to the two different purification treatments described below to prepare two types of alkaline developers, alkaline developer X-W1 and alkaline developer X-W2.Also, alkaline developer Y was subjected to the purification treatment described below to prepare alkaline developer Y-W1.

[0182] Alkaline developer X: 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) Alkaline developer Y: an aqueous solution containing 2.38% by mass of tetramethylammonium hydroxide (TMAH) and a surfactant

[0183] Next, alkaline developer X was filtered through a POU filter in a coater under the two conditions shown below to obtain alkaline developer X-W1 and alkaline developer X-W2, which were used in the examples described later. Similarly, alkaline developer Y was treated using the same procedure to obtain alkaline developer Y-W1, which was used in the examples described later. The term "POU (Point Of Use) filter" refers to a filter installed in the device for purification immediately before use. (Alkaline developer X-W1) POU filtration using Entegris 10nm pore size polyethylene filters (Alkaline developer X-W2) POU filtration using Entegris 20nm pore size polyethylene filters (Alkaline developer Y-W1) POU filtration using Entegris 10nm pore size polyethylene filters

[0184] [Evaluation of the cleanliness of alkaline developer (removal solvent) (measurement of the number of defects caused by the removal solvent used in process X2) (applicable to processes Z1 to Z4)] <Inspection of defects on test wafers> Using a dark-field defect inspection device SP5 manufactured by KLA Tencor, defect inspection was performed on the 12-inch (300 mm diameter) silicon wafers used for the inspection, and the number of defects (defect count) that were 20 nm or larger in size and present on the surface of the silicon wafers was measured ("EX: Number of defects on original substrate").

[0185] In the measurement of the number of defects on the surface of a 12-inch (300 mm diameter) silicon wafer using a dark-field defect inspection system SP5 manufactured by KLA Tencor Corporation, as described below, the number of defects was measured on concentric circles of the 12-inch (300 mm diameter) silicon wafer with an area of ​​660 cm. 2 The area within the circle (in other words, the circle centered on the center of the 12-inch (300 mm diameter) silicon wafer and having an area of ​​660 cm 2 The area inside the circle is the inspection area. In addition, in each table shown below, the number of defects on the surface of a 12-inch (300 mm diameter) silicon wafer is measured using a dark-field defect inspection system SP5 manufactured by KLA Tencor Corporation. The number of defects in the circled area (unit: pieces) and the number of defects per unit area (unit: pieces / cm 2 ) is shown.

[0186] <Evaluation of the cleanliness of alkaline developer (removal solvent) (measurement of the number of defects caused by the removal solvent used in process X2)> The above-mentioned removal solvents (unfiltered) were each connected to the development line of a Cleantrac ACT12 coater manufactured by Tokyo Electron Ltd. When connecting, the above-mentioned POU filter was connected to the connecting piping. That is, the above-mentioned alkaline developers X-W1, X-W2, and X-W3 refer to the alkaline developers obtained by passing through this POU filter, and in the procedure described below, the filtered removal solvents, alkaline developers X-W1, X-W2, and X-W3, are applied onto silicon wafers. Next, the removal solvent connected by the above-mentioned method was applied to a 12-inch (300 mm diameter) silicon wafer that had previously been inspected for defects in the above-mentioned <Defect inspection of inspection wafer> using a coater (discharged at a flow rate of 600 mL / min for 90 seconds), and then baked at 100°C for 60 seconds. For the wafers obtained by the above procedure after application of the removal solvent, the number of defects (defect count) having a size of 20 nm or more present on the surface of the silicon wafer was measured using a dark-field defect inspection device SP5 manufactured by KLA Tencor Corporation ("F: Number of defects after application of the removal solvent"). Next, based on the results of "EX: number of defects in original substrate" and "F: number of defects after application of removal solvent" obtained by the above various inspections, "C: number of defects in removal solvent" was calculated using the following formula. The results are shown in Table 1. Formula (A1): [C: Number of defects in removal solvent] = [F: Number of defects after application of removal solvent] - [EX: Number of defects in original substrate]

[0187] According to the above test, the initial defect count ([C: number of defects in the removal solvent]) of the alkaline developer X-W1 was 100 or less (0.15 / cm 2 The initial number of defects ([C: number of defects in the removal solvent]) for alkaline developer X-W2 was 220 (0.33 / cm 2 ), and the initial defect count ([C: number of defects in the removal solvent]) of the alkaline developer Y-W1 is 100 or less (0.15 / cm 2 It was confirmed that

[0188] [Testing of Resist Composition: Example 1] [Inspection of wafer defects (corresponding to process Y1)] Prior to the evaluation of defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) was inspected for defects using a dark-field defect inspection system SP5 manufactured by KLA Tencor Corporation, and the number of defects (defect count) with a size of 20 nm or more present on the surface of the silicon wafer was measured ("E: Number of defects on original substrate"). The results are shown in Table 1.

[0189] [Formation of resist film (corresponding to process X1)] The prepared resist composition A-2 was connected to the resist line of a coater of a Cleantrac ACT12 manufactured by Tokyo Electron Ltd. (when connecting, no filter was connected to the connecting pipe, but a dummy capsule was used). Next, the resist composition bonded by the above-mentioned method was applied to the above-mentioned 12-inch (300 mm diameter) silicon wafer using a coater, and then baked at 90°C for 90 seconds to form a coating film. The thickness of the resist film (coating film) at this time was adjusted to 80 nm. As mentioned above, no exposure treatment was performed in the above process. Furthermore, the substrate on which the resist film was formed was stored in a wafer case environment in a clean room until it was subjected to the subsequent [resist film removal process (corresponding to process X2)].

[0190] [Resist film removal process (corresponding to process X2)] Next, the resist film is removed from the silicon wafer with the resist film obtained by carrying out the procedure of [Formation of Resist Film (corresponding to Step X1)] using an alkaline developer (removal solvent). The removal solvent used here is the alkaline developer X-W1 described in [Preparation of Alkaline Developer (Removal Solvent Used in Step X2)].

[0191] The removal was carried out in the same manner as in the above-mentioned [Evaluation of the cleanliness of alkaline developer (removal solvent) (measurement of the number of defects caused by the removal solvent used in process X2)], using a Clean Track ACT12 manufactured by Tokyo Electron Ltd., to which the removal solvent before filtration was connected (note that, when connecting, the above-mentioned POU filter was connected to the connecting piping. In other words, the above-mentioned alkaline developer X-W1 refers to the alkaline developer obtained by passing through this POU filter, and in the procedure described below, the filtered removal solvent, alkaline developer X-W1, is applied to the silicon wafer). The specific removal procedure was as follows: the removal solvent was applied to the silicon wafer with the resist film by the coater connected to the development line of the coater using the method described above (discharged at a flow rate of 600 mL / min for 90 seconds), and then the wafer was baked at 100°C for 60 seconds.

[0192] [Inspection of defects on the substrate after removal (corresponding to process X3)] <Evaluation of the number of resist defects (calculation of [A: number of resist defects])> After the above processing, the wafers were subjected to defect inspection using a dark-field defect inspection system SP5 manufactured by KLA Tencor Corporation, and the number of defects (defect count) with a size of 20 nm or more present on the surface of the silicon wafer was measured ([D: Total number of defects after solvent removal processing]).

[0193] Next, based on the results of "E: Number of defects in the original substrate," "D: Total number of defects after solvent removal treatment," and "C: Number of defects in the removal solvent" obtained from the various tests described above, "A: Number of resist defects" was calculated using the following formula. Formula (A2): [A: Number of resist defects] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects on original substrate] - [C: Number of defects in removal solvent] The results are shown in Table 1.

[0194] [Testing of Resist Composition: Example 2] The resist composition of Example 2 was tested in the same manner as in Example 1, except that resist composition A-2 was used instead of resist composition A-1. The results are shown in Table 1.

[0195] [Testing of Resist Composition: Example 3] The resist composition of Example 3 was tested in the same manner as in Example 1, except that resist composition A-1 was replaced with resist composition B-1. The results are shown in Table 1.

[0196] [Testing of Resist Composition: Example 4] The resist composition of Example 4 was inspected in the same manner as in Example 3, except that the defect inspection of the inspection wafer (corresponding to step Y1) was not performed. The results are shown in Table 1. In Example 4, based on the results of [D: total number of defects after solvent removal process] and [C: number of defects in the removal solvent] obtained from the various tests described above, "AX: number of resist defects" was calculated using the following formula. Formula (A3): "AX: Number of resist defects" = [D: Total number of defects after solvent removal treatment] - [C: Number of defects in removal solvent]

[0197] [Testing of Resist Composition: Example 5] The resist composition of Example 5 was tested in the same manner as in Example 3, except that the removal solvent was changed to the alkaline developer X-W2 described in [Preparation of alkaline developer (removal solvent used in step X2)]. The results are shown in Table 1.

[0198] [Testing of Resist Composition: Example 6] Except for changing the type of substrate, the resist composition of Example 6 was tested in the same manner as in Example 3. The results are shown in Table 1.

[0199] [Testing of Resist Composition: Example 7] The resist composition of Example 7 was tested in the same manner as in Example 3, except that resist composition B-1 was replaced with resist composition B-2A. The results are shown in Table 1.

[0200] [Testing of Resist Composition: Example 8] The resist composition of Example 8 was tested in the same manner as in Example 3, except that resist composition B-1 was replaced with resist composition B-2B. The results are shown in Table 1.

[0201] [Testing of Resist Composition: Example 9] The resist composition of Example 9 was tested in the same manner as in Example 3, except that the removal solvent was changed to the alkaline developer Y-W1 described in [Preparation of alkaline developer (removal solvent used in step X2)]. The results are shown in Table 1.

[0202] [Inspection of Resist Composition: Comparative Example 1] After the formation of the resist film (corresponding to process X1), and before the removal of the resist film (corresponding to process X2), exposure processing (80 uC / cm 2 The resist composition of Comparative Example 1 was inspected in the same manner as in Example 3, except that irradiation was performed. The results are shown in Table 1.

[0203] [Inspection of Resist Composition: Comparative Example 2] The resist composition of Comparative Example 2 was tested in the same manner as in Example 3, except that resist composition B-1 was replaced with resist composition C-1. The results are shown in Table 1.

[0204] Table 1 is shown below. In the table, the numbers in the column "Number of initial defects on the substrate [Number of defects 20 nm or larger] ("E: Number of defects on the original substrate")" represent the number of defects measured in the above-mentioned "defect inspection of the inspection wafer (corresponding to process Y1)." In addition, in the table, the value in the column "Number of initial defects in alkaline developer [Number of defects of 20 nm or more] ([C: Number of defects in removing solvent])" represents the number of defects measured in the above-mentioned <Evaluation of cleanliness of alkaline developer (removing solvent) (measurement of number of defects caused by the removing solvent used in step X2)>. In the table, in the column "Number of defects (other than Example 4; [A: number of resist defects], Example 4; [AX: number of resist defects])," [A: number of resist defects] other than Example 4 is a numerical value obtained by formula (A2) ([D: total number of defects after solvent removal treatment] - [E: number of defects in original substrate] - [C: number of defects in removal solvent]). [AX: number of resist defects] in Example 4 is a value obtained by the formula (A3) ([D: total number of defects after solvent removal treatment] - [C: number of removal solvent defects]) as described above.

[0205] In addition, in the table, the "Whether or not exposure was performed" column indicates whether or not exposure processing was performed after [forming the resist film (corresponding to process X1)] and before performing [the resist film removal process (corresponding to process X2)]. In the table, the "resist remaining film" column indicates whether or not there is a remaining film after the resist film removal process (corresponding to process X2). "No" indicates that no remaining film was visually confirmed after the resist film removal process (corresponding to process X2), and "Yes" indicates that a remaining film was visually confirmed.

[0206] [Table 1]

[0207] It is known that the number of defects occurring on a substrate due to foreign matter in the resist composition can be reduced by reducing the filter diameter, increasing the number of circulations, pre-cleaning the filter, etc. Therefore, in the evaluation of the inspection method of the example, if [A: number of resist defects] is consistent with the ranking of the number of potential defects described above and the difference is clear, it can be considered that even minute foreign matter in the resist composition has been evaluated. The results in Table 1 show that the inspection method of the present embodiment can evaluate even minute foreign matter. For example, the number of potential defects for the resist compositions used in Examples 1 to 3 appears to decrease in the following order: resist composition A-1 (filtered product obtained by combining Filter C and Filter D) > A-2 (filtered product obtained by combining Filter A and Filter B) > B-1 (filtered product obtained by combining Filter A and Filter B). In contrast, the numbers of defects ([A: number of resist defects]) for Examples 1 to 3 are consistent with the ranking of potential defects, and the differences between them are clear. Furthermore, the numbers of potential defects for the resist compositions used in Examples 3, 7, and 8 appear to decrease in the following order: B-1 (filtered product obtained by combining Filter A and Filter B once) > B-2A (filtered product obtained by combining Filter A and Filter B 14 times) > B-2B (filtered product obtained by combining Filter A and Filter B 14 times after pre-cleaning). In contrast, the numbers of defects ([A: number of resist defects]) for Examples 3, 7, and 8 are consistent with the ranking of potential defects, and the differences between them are clear.

[0208] Furthermore, a comparison between Examples 3 and 4 confirmed that when the inspection method includes process Y1, more accurate defect evaluation can be performed without being affected by the initial number of defects on the substrate ("E: number of defects on the original substrate").

[0209] Furthermore, a comparison between Example 3 and Example 5 confirmed that when the number of initial defects ([C: number of removal solvent defects]) in the removal solvent used in step X2 is large, it affects the defect inspection of the substrate after removal (corresponding to step X3). (Even when a correction is made by subtracting the number of initial defects ([C: number of removal solvent defects]) in the removal solvent used in step X2, a lot of scattered light originating from defects in the alkaline developer occurs during the defect inspection of the substrate after removal, and the value of [A: number of resist defects] tends to be large.) From this result, it can be seen that when the number of initial defects ([C: number of removal solvent defects]) in the removal solvent used in step X2 is small (preferably, the number of defects of 20 nm or more is 0.15 / cm). 2 It was confirmed that more accurate defect evaluation can be performed when the

[0210] Furthermore, a comparison between Example 3 and Example 6 confirmed that when the number of initial defects in the substrate used in step X1 ("E: number of defects in the original substrate") is large, it affects the defect inspection of the substrate after removal (corresponding to step X3) (even when a correction is made by subtracting the number of initial defects in the substrate used in step X1 ("E: number of defects in the original substrate"), a lot of scattered light originating from defects in the substrate occurs during the defect inspection of the substrate after removal, and the value of [A: number of defects in the resist] tends to be large). From this result, it can be seen that when the number of initial defects in the substrate used in step X1 ("E: number of defects in the original substrate") is small (preferably, the number of defects of 20 nm or more is 0.15 / cm), the number of defects is small (preferably, the number of defects of 20 nm or more is 0.15 / cm). 2 It was confirmed that more accurate defect evaluation can be performed when the

[0211] In the inspection method of the comparative example, the resist film remained, making it impossible to inspect the substrate for defects. Although it is possible to inspect the remaining resist film for defects, the inspection method typically targets defects of 40 nm or larger in size.

[0212] [Inspection of Resist Composition (LPC): Comparative Examples 3 to 11] For each of the resist compositions used in Examples 1 to 9 in Table 1 above, the number of particles with a particle size of 0.15 μm or more (LPC) contained in 1 mL of the composition was measured using a particle counter manufactured by Rion Co., Ltd. The results are shown in Table 2.

[0213] [Table 2]

[0214] In Comparative Examples 3 to 11 (LPC (liquid-borne particle) evaluation), only large defects of 0.15 μm (150 nm) or more could be evaluated, and the difference in the number of fine defects between the three resist compositions using different filtration methods described above could not be evaluated. Furthermore, even when tests were conducted using the same resist composition, there was variation in the number of defects observed.

Claims

1. A method for testing an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component, comprising: A step X1 of applying the composition to a substrate to form a coating film; a step X2 of removing the coating film from the substrate using an alkaline developer without performing an exposure treatment by irradiation with actinic rays or radiation; and a step X3 of measuring the number of defects on the substrate after removing the coating film using a defect inspection device, The inspection method, wherein the alkaline developer used in the step X2 is an alkaline developer in which the number of defects having a size of 20 nm or more calculated by the following defect inspection R1 is 0.15 / cm 2 or less. Defect inspection R1: The defect inspection R1 includes the following steps ZA1 to ZA4. Step ZA1: A step of measuring the number of defects on the substrate that are 20 nm or larger in size using a defect inspection device. Step ZA2: applying the alkaline developer to the substrate Step ZA3: A step of measuring the number of defects having a size of 20 nm or more on the substrate coated with the alkaline developer using a defect inspection device. Step ZA4: A step of calculating the number of defects having a size of 20 nm or more resulting from the alkaline developer by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3.

2. A method for inspecting an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component, comprising: A step X1 of applying the composition to a substrate to form a coating film; a step X2 of removing the coating film from the substrate using an alkaline developer without performing an exposure treatment by irradiation with actinic rays or radiation; a step X3 of measuring the number of defects on the substrate after removing the coating film using a defect inspection device; An inspection method comprising any one selected from the group consisting of step X3B, step X3C, and step X3D. Step X3B: A step of calculating the number of defects derived from the composition by subtracting the number of defects present on the substrate before applying the step X1 from the number of defects measured in the step X3. Step X3C: A step of calculating the number of defects derived from the composition by subtracting the number of defects derived from the alkaline developer from the number of defects measured in the step X3. Step X3D: A step of calculating the number of defects derived from the composition by subtracting the number of defects present on the substrate before application to the step X1 and the number of defects derived from the alkaline developer from the number of defects measured in the step X3.

3. Furthermore, before the step X2, a step Z1 of applying the alkaline developer used in the step X2 to a substrate; 3. The inspection method according to claim 2, further comprising a step Z2 of measuring the number of defects on the substrate coated with the alkaline developer using a defect inspection device.

4. Furthermore, before the step Z1, a step Z3 is performed in which the number of defects on the substrate to be used in the step Z1 is measured using a defect inspection device; and step Z4 of calculating the number of defects resulting from the alkaline developer used in step Z2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2.

5. The inspection method according to any one of claims 2 to 4, wherein the alkaline developer used in step X2 is an alkaline developer in which the number of defects having a size of 20 nm or more calculated by the following defect inspection R1 is 0.15 / cm2 or less. Defect inspection R1: The defect inspection R1 includes the following steps ZA1 to ZA4. Step ZA1: A step of measuring the number of defects on the substrate that are 20 nm or larger in size using a defect inspection device. Step ZA2: applying the alkaline developer to the substrate Step ZA3: A step of measuring the number of defects having a size of 20 nm or more on the substrate coated with the alkaline developer using a defect inspection device. Step ZA4: A step of calculating the number of defects having a size of 20 nm or more resulting from the alkaline developer by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3.

6. 6. The inspection method according to claim 1, further comprising, before the step X1, a step Y1 of measuring the number of defects on the substrate used in the step X1 using a defect inspection device.

7. In the step X1, the substrate is a silicon wafer, and the number of defects measured using a defect inspection device is 0.15 / cm. ２ The inspection method according to any one of claims 1 to 6, wherein:

8. In the step X1, the substrate is a silicon wafer, and the number of defects having a size of 20 nm or more on the substrate measured using a defect inspection device is 0.15 / cm ２ The inspection method according to any one of claims 1 to 7, wherein:

9. 9. The inspection method according to claim 1, wherein the alkaline developer is an aqueous solution containing tetramethylammonium hydroxide.

10. 10. The inspection method according to claim 1, wherein in the step X2, the removal time of the removal treatment using the alkaline developer is 300 seconds or less.

11. The inspection method according to claim 10, wherein the removal time is 180 seconds or less.

12. A method for testing an actinic ray-sensitive or radiation-sensitive composition containing an alkali-soluble component, comprising: A step X1 of applying the composition to a substrate to form a coating film; a step X2 of removing the coating film from the substrate using an alkaline developer without performing an exposure treatment by irradiation with actinic rays or radiation; a process X3A of measuring the number of defects on the substrate after removing the coating film using a defect inspection device; Furthermore, before the step X1, a step Y1 of measuring the number of defects on the substrate to be used in the step X1 using a defect inspection device; Before the step X2, a step Z1 of applying the alkaline developer used in the step X2 to a substrate; a step Z2 of measuring the number of defects on the substrate coated with the alkaline developer using a defect inspection device; a process Z3 in which the number of defects on the substrate used in the process Z1 is measured using a defect inspection device; a step ZX for carrying out a step Z4 for calculating the number of defects resulting from the alkaline developer used in the step X2 by subtracting the number of defects measured in the step Z3 from the number of defects measured in the step Z2; and a step X3E of calculating the number of defects derived from the composition by subtracting the number of defects calculated in the step Y1 and the number of defects calculated in the step Z4 from the number of defects measured in the step X3A.

13. preparing an actinic ray- or radiation-sensitive composition; A method for producing an actinic ray-sensitive or radiation-sensitive composition, comprising: a step of carrying out the inspection method according to any one of claims 1 to 12.

14. A method for manufacturing an electronic device, comprising a step of carrying out the inspection method according to any one of claims 1 to 12.

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