Testing method, method for manufacturing the composition, method for testing the composition

Abstract

The present invention provides an inspection method for readily measuring ultra-small foreign matter in a composition selected from the group consisting of an active-ray-sensitive or radiation-sensitive composition and a thermosetting composition. The present invention also provides a method for manufacturing a composition and a method for verifying a composition, in which the abovementioned inspection method is used. The inspection method is a method for inspecting a composition selected from the group consisting of an active-ray-sensitive or radiation-sensitive composition and a thermosetting composition. The inspection method includes: a step X1 for forming a film by applying the abovementioned composition to a substrate X; a step X2 for removing the film from the substrate X by using a removal solvent containing an organic solvent; and a step X3 for measuring the number of defects on the substrate X after the removal of the film by using a defect inspection device. When the abovementioned composition is an active-ray-sensitive or radiation-sensitive composition, the abovementioned step X2 is applied in a state where the film has not been subjected to exposure treatment by means of irradiation with active rays or radiation. When the abovementioned composition is a thermosetting composition, the abovementioned step X2 is applied in a state where the film has not been subjected to thermosetting treatment.

Description

Technical Field

[0001] The present invention relates to an inspection method, a method for manufacturing a composition, and a method for assaying a composition.

Background Art

[0002] It is known that semiconductor devices are manufactured by forming a fine electronic circuit pattern on a substrate using photolithography technology. Specifically, after forming a resist film obtained using a chemically amplified photosensitive or radiation-sensitive composition (hereinafter also referred to as a "resist composition") on a substrate, exposure treatment of irradiating the resist film with light, development treatment using a developer, and various treatments such as rinsing treatment using a rinse liquid as necessary are performed to obtain a patterned resist film. Using the patterned resist film thus obtained as a mask, various treatments are performed to form an electronic circuit pattern. In such a semiconductor device forming process, in order to further improve the yield of the semiconductor devices obtained, a pattern forming method capable of suppressing the occurrence of defects is required. In recent years, the manufacture of semiconductor devices with a node size of 10 nm or less has been under consideration, and this tendency has become even more prominent.

[0003] By the way, one of the causes of defects in the pattern is foreign matter contained in the resist composition. Conventionally, as a method for inspecting the presence and number of foreign matter contained in a resist composition, a method of measuring foreign matter in a resist composition (solution) using a liquid particle counter (for example, a fine particle measuring instrument of 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 observing this coating film with a defect inspection device (for example, a dark field defect inspection device: manufactured by KLA-Tencor Corporation, Surfscan (registered trademark) SP5, etc.) to measure foreign matter on the film surface and in the film have been implemented. However, in methods using a liquid particle counter to measure foreign matter in a resist composition (solution), the detection limits of the equipment typically make it difficult to detect particles smaller than 0.1 μm (100 nm). Similarly, in methods using defect inspection equipment to measure foreign matter on the film surface and within the film, defects of 40 nm to 60 nm in size are typically the target of detection. Therefore, these inspection methods lack sufficient detection sensitivity for application in the manufacturing of semiconductor devices with a 10 nm node or smaller.

[0004] Furthermore, inspection methods for detecting foreign substances in resist compositions are not limited to those described above, and various studies have been conducted to date. For example, Patent Document 1 discloses a method for detecting gel-like foreign matter that induces pattern defects, characterized by comprising the steps of: rotating and coating a photoresist onto a semiconductor substrate; exposing the coated photoresist using ultraviolet light; removing the photosensitive 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 the scattered light. Specifically, Patent Document 1 exposes the substrate by performing exposure and alkaline development on a positive-type resist film formed from a positive-type resist composition, and detects the presence or absence of gel-like substance in the resist composition by measuring the gel-like foreign matter adhering to the exposed substrate.

[0005] In the section above, foreign matter contained in the resist composition was cited as one of the causes of defects in the pattern. However, defects in the pattern can be caused not only by the resist composition but also by foreign matter contained in various thermosetting compositions used during pattern formation (for example, BARC (anti-reflective coating), SOC (spin-on carbon coating), SOG (spin-on glass coating), TARC (anti-reflective coating), and immersion topcoat materials, etc.). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 07-280739 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present inventors investigated the foreign matter inspection method described in Patent Document 1 and found that in the method described in Patent Document 1, since the substrate defect inspection is performed after exposure and alkaline development of the positive-type resist film, a reaction occurs in the components of the resist film during exposure, and there is a risk that the defect components may also be altered as a result. In other words, the inventors have clarified that the detection accuracy of the inspection method, which performs substrate defect inspection after exposure of the resist film, may be insufficient for foreign matter inspection of the resist composition, and that there is room for improvement.

[0008] Furthermore, as mentioned above, the inspection method must also exhibit sufficient detection sensitivity when applied to the manufacturing of modern, miniaturized semiconductor devices (in other words, it must be able to measure even minute foreign objects).

[0009] Therefore, the object of the present invention is to provide a simple inspection method for measuring minute foreign matter in a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions. Furthermore, the present invention also aims to provide a method for producing a composition using the above-described inspection method and a method for testing a composition. [Means for solving the problem]

[0010] The inventors have found that the above problems can be solved by the following configuration.

[0011] [1] A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, Step X1 involves applying the above composition to a substrate X to form a coating film, Step X2 involves removing the coating film from the substrate X using a removal solvent containing an organic solvent, The process includes step X3 of measuring the number of defects on the substrate X after removing the above coating using a defect inspection device, If the above composition is a light-sensitive or radiation-sensitive composition, step X2 is performed when the coating film has not been exposed to light or radiation. If the above composition is a thermosetting composition, step X2 is an inspection method applied when the coating film has not undergone thermosetting treatment. [2] Furthermore, the process has a step Y1 prior to the above step X1, The inspection method according to [1], wherein step Y1 is a step of measuring the number of defects on the substrate X used in step X1 using the defect inspection device. [3] The substrate X is a silicon wafer, and the number of defects measured in step Y1 is 0.75 per cm². 2 The following is the testing method described in [2]. [4] The substrate X is a silicon wafer, and the number of defects with a size of 19 nm or more on the substrate X measured in step Y1 is 0.75 defects / cm². 2 The following is the inspection method described in [2] or [3]. [5] The number of defects larger than 19 nm is 0.15 per cm². 2 The following is the testing method described in [4]. [6] Furthermore, step Z1 involves applying the above-mentioned removal solvent to the substrate Z, The inspection method according to any one of [1] to [5], further comprising step Z2 of measuring the number of defects on the substrate Z to which the above-mentioned removal solvent has been applied using the above-mentioned defect inspection device. [7] Furthermore, prior to step Z1, step Z3 is performed on the substrate Z using the defect inspection device to measure the number of defects on the substrate Z, The inspection method according to [6], comprising: step Z4, which calculates the number of defects originating from the removal solvent used in step X2 by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2. [8] The removal solvent used is such that the number of defects with a size of 19 nm or larger calculated in the defect inspection R1 below is 1.50 per cm. 2 The following testing method is one of the following: [1] to [7]. Defect inspection R1: Defect inspection R1 has the following steps ZA1 to ZA4. Process ZA1: A process of measuring the number of defects with a size of 19 nm or larger on the substrate ZA using the above defect inspection device. Step ZA2: Step of applying the above-mentioned removal solvent to the substrate ZA. Step ZA3: A step in which the number of defects with a size of 19 nm or larger on the substrate ZA to which the above-mentioned removal solvent has been applied is measured using the above-mentioned defect inspection device. Step ZA4: A step to calculate the number of defects of size 19 nm or larger that originate from the removal solvent by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3. [9] The number of defects larger than 19 nm is 0.75 per cm². 2 The following is the testing method described in [8].

[10] The inspection method according to any one of [1] to [9], wherein the above-mentioned organic solvent includes one or more selected from the group consisting of ester-based organic solvents, alcohol-based organic solvents, and ketone-based organic solvents.

[11] The test method according to any one of [1] to

[10] , wherein the above organic solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

[12] The inspection method according to any one of [1] to

[11] , wherein in step X2 above, the removal time of the removal treatment using the removal solvent is 300 seconds or less.

[13] The inspection method described in

[12] , wherein the removal time is 60 seconds or less.

[14] The inspection method according to any one of [1] to

[13] , wherein in step X2, the removal solvent contains two or more organic solvents.

[15] A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, Step X1 involves applying the above composition to a substrate X to form a coating film, Step X2 involves removing the coating film from the substrate X using a removal solvent containing an organic solvent, Step X3A involves measuring the number of defects on the substrate X after removing the coating using the defect inspection device, Furthermore, prior to the above-mentioned process X1, there are processes Y1 and ZX, If the above composition is a light-sensitive or radiation-sensitive composition, step X2 is performed when the coating film has not been exposed to light or radiation. If the above composition is a thermosetting composition, step X2 is applied when the coating film has not undergone thermosetting treatment. Step Y1 described above is a step of measuring the number of defects on the substrate X using the defect inspection device described above. The above process ZX includes process Z1 of applying the above removal solvent to the substrate ZX, Step Z2 involves measuring the number of defects on the substrate ZX to which the above-mentioned removal solvent has been applied using the above-mentioned defect inspection device. Step Z3 involves measuring the number of defects on the substrate ZX using the defect inspection device described above. The process includes step Z4, which calculates the number of defects originating from the removal solvent by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2. The inspection method according to [1], comprising step X3E, which calculates the number of defects originating from the composition by subtracting the number of defects measured in step Y1 and the number of defects calculated in step Z4 from the number of defects measured in step X3A.

[16] A step of preparing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, A method for producing a composition, comprising the step of carrying out one of the inspection methods described in [1] to

[15] .

[17] A method for producing the composition according to

[16] , wherein the composition is a photosensitive or radiation-sensitive composition.

[18] A method for testing a composition, which includes the testing method described in any of [1] to

[14] , The above inspection method includes a step of obtaining the number of defects on the substrate after removing the coating, A method for testing a composition, comprising the step of comparing the number of defects obtained with reference data to determine whether it is within an acceptable range.

[19] A method for testing a composition, including the testing method described in

[15] , The above inspection method includes a step of obtaining the number of defects originating from the above composition, A method for testing a composition, comprising the step of comparing the number of defects obtained with reference data to determine whether it is within an acceptable range.

[20] The standard value based on the above standard data is 0.75 pieces / cm 2 The following is a method for testing the composition described in

[18] or

[19] .

[21] A step of preparing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, A method for producing a composition, comprising the step of carrying out one of the testing methods described in

[18] to

[20] . [Effects of the Invention]

[0012] According to the present invention, a simple inspection method can be provided for measuring minute foreign matter in a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions. Furthermore, according to the present invention, it is possible to provide a method for producing a composition using the above-described inspection method and a method for testing a composition. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, the substituents are preferably monovalent. In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this specification, "light" means active light or radiation. In this specification, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet and extreme ultraviolet light represented by excimer lasers, and X-rays, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. The bonding direction of divalent groups as expressed herein is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0014] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also called molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M, manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0015] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. All pKa values ​​described herein are those calculated using this software package.

[0016] Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0017] On the other hand, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + One method is to calculate it by calculating the dissociation free energy. + The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this method. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0018] In this specification, pKa refers to a value calculated using software package 1 based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. Furthermore, as stated above, pKa refers to "pKa in aqueous solution," but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used.

[0019] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0020] In this specification, "solids" refers to all components other than the solvent. Even if the solids are in a liquid state, they will be included in the calculation.

[0021] [Testing Method] The inspection method of the present invention is A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions (hereinafter also referred to as "resist compositions") and thermosetting compositions (hereinafter also referred to as "test compositions"), comprising the following steps X1 to X3. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a photosensitive or radiation-sensitive composition, this step removes the coating film from the substrate X using a removal solvent containing an organic solvent (hereinafter also referred to as "removal solvent") without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step removes the coating film from the substrate X using a removal solvent containing an organic solvent (hereinafter also referred to as "removal solvent") without thermosetting treatment. Step X3: A step in which the number of defects on the substrate X after the above coating film has been removed is measured using a defect inspection device.

[0022] A key feature of the above inspection method is that it detects foreign substances contained in the inspection composition on the substrate. The mechanism of action will be explained below. In the above inspection method, in step X1, the inspection composition is temporarily formed as a coating film on the substrate X, and in the subsequent step X2, a removal process is performed to remove the coating film from the substrate X using a removal solvent. As a result of the removal process, due to the elution of the coating film into the removal solvent, minute foreign matter (foreign matter that may cause defects after pattern formation) contained in the coating film may adhere to the surface of the substrate X after step X2. In the inspection method of the present invention, in step X3, the number of defects present on the surface of the substrate X after step X2 is measured. In other words, the inspection method of the present invention detects foreign matter contained in the inspection composition as defects on the substrate X. For defects present on the surface of a substrate such as a silicon wafer for semiconductor manufacturing, it is possible to measure defects as small as approximately 19 nm in size using commercially available defect inspection equipment (for example, dark-field defect inspection equipment: Surfscan® SP5 manufactured by KLA-Tencor, etc.). Therefore, compared to the methods described above for measuring foreign matter in a resist composition (solution) using a liquid particle counter (detection limit / target: typically particles with a particle size of 0.1 μm (100 nm) or larger), and for measuring foreign matter on the film surface and within the film using a defect inspection device (detection limit / target: typically defects with a size of 40 nm to 60 nm), this method can detect even smaller foreign matter. Hereinafter, the number of defects measured using the above-mentioned defect detection device in each process will also be referred to as the "number of defects" or "defect count."

[0023] Therefore, according to the above inspection method, minute foreign substances in a composition (inspection composition) selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions can be easily measured. Furthermore, since the above inspection method does not involve alteration of the inspection composition due to exposure or thermosetting (specifically, alteration of compounds and defects in the inspection composition), it can be said that, compared to the inspection method of Patent Document 1, it is a method that can capture defects actually contained in the inspection composition more effectively (has superior detection accuracy).

[0024] The inspection method of the present invention will be described below with reference to a specific embodiment. In the following description of the inspection method, an example will be given in which the size of the defect measured using the defect inspection device is 19 nm or larger, but the size of the defect is not limited thereto. If the detection limit of the device is acceptable, defects smaller than 19 nm may also be subject to inspection.

[0025] [First embodiment of the inspection method] The first embodiment of the inspection method is an inspection method for a composition (inspection composition) selected from the group consisting of resist compositions and thermosetting compositions, and comprises the following steps X1 to X3. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a resist composition, this step involves removing the coating film from the substrate X using a removal solvent containing an organic solvent (removal solvent) without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step involves removing the coating film from the substrate X using a removal solvent containing an organic solvent (removal solvent) without thermal curing treatment. Step X3: A step of measuring the number of defects on the substrate X after removing the coating using a defect inspection device.

[0026] Below, we will first explain each step.

[0027] <<Process X1>> Step 1 is the process of forming a coating film on a substrate X using the composition to be inspected in this inspection method (inspection composition). Here, the inspection composition is a resist composition or a thermosetting composition. The following describes the various materials used in process X1 and the procedure for process X1.

[0028] <Various materials> (Test composition) Resist compositions and thermosetting compositions that are suitably applicable to this inspection method will be described later.

[0029] (Substrate X, Substrate Z, and Substrate ZA) Examples of Substrate X include substrates used in the manufacture of integrated circuit elements, with silicon wafers being preferred. In terms of further improving inspection accuracy, the number of defects (original substrate defect count) existing on Substrate X before being applied to Step X1 should preferably be 1.20 defects / cm 2 or less, more preferably 0.75 defects / cm 2 or less, and even more preferably 0.15 defects / cm 2 or less. The lower limit is, for example, 0.00 defects / cm 2 or more. Among these, in terms of further improving inspection accuracy, the number of defects with a size of 19 nm or more existing on Substrate X before being applied to Step X1 should preferably be 1.20 defects / cm 2 or less, more preferably 0.75 defects / cm 2 or less, and even more preferably 0.15 defects / cm 2 or less. The lower limit is, for example, 0.00 defects / cm 2 or more. There is no particular upper limit for the size of the defects, but for example, it is 5 μm or less, and the same applies to the defects described in each step below. When the number of defects on Substrate X used in Step X1 is large, scattering may occur during the defect inspection on the substrate performed in Step X3, which may prevent accurate measurement of the number of defects. Therefore, in terms of the defect inspection accuracy on the substrate in Step X3 being more excellent (and thus the inspection accuracy of this inspection method being further improved), it is preferable to use a Substrate X with a high cleanliness level (a small number of original substrate defects). The defect inspection on Substrate X can be measured using a defect inspection device (e.g., a dark-field defect inspection device: Surfscan (registered trademark) SP5 manufactured by KLA-Tencor Corporation, etc.). The specifications for substrates Z and ZA are the same as those for substrate X described above. Furthermore, the preferred configurations for substrates Z and ZA, as well as the preferred configurations for each process described later, are the same as those for substrate X. The following configurations are preferred examples of substrates X, Z, and ZA in terms of providing superior accuracy in defect inspection on the substrates (and consequently, improving the inspection accuracy of this inspection method). Substrates X, Z, and ZA are wafers made of the same material. Substrates X, Z, and ZA are wafers made from ingots manufactured using the same method. Substrates X, Z, and ZA are wafers made from ingots from the same manufacturing lot.

[0030] <Process X1> One method for forming a coating film on a substrate X using the inspection composition is to apply the inspection composition onto the substrate X. Other examples of application methods include applying the coating using a coater cup and applying the coating using an organic developing unit. It is also preferable to use a spin coating method using a spinner. The rotation speed when performing spin coating using a spinner is preferably 500 to 3000 rpm. It is preferable to apply the inspection composition onto the substrate X and then dry the substrate X. As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out 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, it is preferable to heat at 100°C for 60 seconds.

[0031] The film thickness of the coating is not particularly limited, but is preferably 10 to 1000 nm, and more preferably 10 to 120 nm. In particular, it is preferable to consider the film thickness for each application of the inspection composition. For example, if the inspection composition is a resist composition and is used for pattern formation by EUV exposure or EB exposure, the film thickness is more preferably 10 to 100 nm, and even more preferably 15 to 70 nm. Also, for example, if the inspection composition is a resist composition and is used for pattern formation by ArF immersion exposure, the film thickness is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0032] <Process X2> Step X2 is a step in which the coating film formed in step X1 is removed from the substrate X using a removal solvent containing an organic solvent (removal solvent). However, in step X2, if the inspection composition is a resist composition, the coating film is removed from the substrate X without exposure (i.e., without causing alteration of the components in the coating film due to exposure). Also, if the inspection composition is a thermosetting composition, the coating film is removed from the substrate X without thermal curing treatment (i.e., without causing alteration of the components in the coating film due to thermal curing treatment). Note that "without exposure if the inspection composition is a resist composition" means that exposure treatment is not performed at an exposure level higher than the minimum exposure level at which residual film is observed. Also, "without thermal curing treatment if it is a thermosetting composition" means that intentional heating treatment is not performed.

[0033] The following describes the various materials used in process X2 and the procedure for process X2.

[0034] (Removal solvent containing organic solvents (removal solvent)) The removal solvent used in process X2 includes an organic solvent. The organic solvent may be a single type or a mixture of multiple types. The content of organic solvents (total if multiple types are mixed) in the removal solvent is preferably 60 to 100% by mass, more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, particularly preferably 95 to 100% by mass, and most preferably 98 to 100% by mass, relative to the total amount of the removal solvent. In particular, the removal solvent is preferably substantially water-free in terms of improving inspection accuracy. "Substantially water-free removal solvent" means that the water content in the removal solvent is 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably water-free.

[0035] The above-mentioned organic solvent is not particularly limited as long as it can remove the coating film formed in step X1 from the substrate X. However, it is preferable that it is an organic solvent contained in the inspection composition (for example, if the inspection composition is a resist composition, then the organic solvent used to dilute the resist component is included). It is preferable that it contains one or more selected from the group consisting of ester-based organic solvents, alcohol-based organic solvents, and ketone-based organic solvents, and it is more preferable that it consists of these groups.

[0036] Examples of ester-based organic solvents include propylene glycol monoalkyl ether carboxylate, lactic acid ester, acetate ester, lactone, and alkoxypropionic acid ester.

[0037] As the propylene glycol monoalkyl ether carboxylate, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, or propylene glycol monoethyl ether acetate are preferred, and propylene glycol monomethyl ether acetate (PGMEA) is more preferred. As the lactic acid ester, ethyl lactate, butyl lactate, or propyl lactate are preferred. Preferred acetate esters include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate. Preferred alkoxypropionate esters include methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP). γ-butyrolactone is preferred as the lactone.

[0038] Examples of alcohol-based organic solvents include propylene glycol monoalkyl ether. As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE) is preferred.

[0039] Examples of ketone-based organic solvents include linear ketones and cyclic ketones. Preferred chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone. As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone are preferred.

[0040] The organic solvent preferably contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, and γ-butyl lactone, and more preferably consists of these.

[0041] The above-mentioned organic solvent may be a single type or a mixture of two or more types. The organic solvent used for removal is preferably a mixed solvent of PGMEA / PGME (for example, a mixed mass ratio of 15 / 85 to 85 / 15).

[0042] In terms of improved inspection accuracy, the removal solvent used in process X2 yields 4.00 defects / cm² when the following defect inspection R1 is performed. 2 The following is preferable. In other words, in terms of improving the accuracy of defect inspection, the removal solvent used in process X2 is preferable if the number of defects calculated in the defect inspection R1 below is 4.00 per cm. 2 The following solvents are preferred. The removal solvent used in process X2 further improves inspection accuracy, achieving a defect rate of 2.30 defects / cm² when the following defect inspection R1 is performed. 2 It is more preferable that the following conditions are met: 1.50 pieces / cm 2 It is even more preferable that the following conditions be met: 0.75 pieces / cm 2 The following is particularly preferable. A lower limit, for example, could be 0.00 pieces / cm². 2 That's all. In terms of improved inspection accuracy, the removal solvent used in process X2, when the defect inspection R1 described below is performed, yields 4.00 defects / cm² with a size of 19 nm or larger. 2 Preferably, the following conditions are met: In other words, in terms of improving the accuracy of defect inspection, the removal solvent used in process X2 should result in 4.00 defects / cm² of defects larger than 19 nm, as calculated in the defect inspection R1 below. 2 The following solvents are preferred. The removal solvent used in process X2 further improves inspection accuracy, resulting in a defect inspection R1 (described below) that detects 2.30 defects / cm² of size larger than 19 nm. 2 It is more preferable that the following conditions are met: 1.50 pieces / cm 2 It is even more preferable that the following conditions be met: 0.75 pieces / cm 2The following is particularly preferable. A lower limit, for example, could be 0.00 pieces / cm². 2 That's all. ≪Defect Inspection R1≫ Defect inspection R1 has the following steps ZA1 to ZA4. Process ZA1: A process of measuring the number of defects on the substrate ZA using a defect inspection device. Process ZA2: Process of applying the removal solvent to the substrate ZA. Step ZA3: A step in which the number of defects on the substrate ZA to which the removal solvent has been applied is measured using a defect inspection device. Process ZA4: A process to calculate the number of defects originating from the removal solvent by subtracting the number of defects measured in process ZA1 from the number of defects measured in process ZA3.

[0043] Furthermore, defect inspection of substrate ZA in processes ZA1 and ZA3 can be performed using defect inspection equipment (for example, dark-field defect inspection equipment: Surfscan® SP5 manufactured by KLA-Tencor, etc.).

[0044] The defect inspection R1 will be explained below. ·Process ZA1 Step ZA1 is a step in which the number of defects on the substrate ZA is measured using a defect inspection device. Specifically, the number of defects present on the substrate ZA (preferably the number of defects with a size of 19 nm or larger) is measured. The substrate ZA used in process ZA1 is not particularly limited, but examples include substrates used in the manufacture of integrated circuit elements, and silicon wafers are preferred. Defect inspection of substrate ZA in process ZA1 can be performed using a defect inspection device (e.g., dark-field defect inspection device: KLA-Tencor's Surfscan® SP5, etc.). By performing the above process ZA1, the number of defects (preferably the number of defects with a size of 19 nm or larger) that exist on the substrate ZA before applying the process ZA2 (original substrate defect count) is measured.

[0045] ·Process ZA2: Step ZA2 is the process of applying a removal solvent to the substrate ZA. There are no particular limitations on the method of applying the removal solvent onto the substrate ZA, 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 10.0 mL / s, and more preferably 0.5 to 3.0 mL / s. The supply time is preferably 3 to 300 seconds, and more preferably 5 to 60 seconds. It is preferable to apply a removal solvent to the substrate ZA and then dry the substrate ZA. As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out 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 60 to 800 seconds, and even more preferably 60 to 600 seconds. In one embodiment, it is preferable to heat at 100°C for 60 seconds.

[0046] ·Process ZA3 Step ZA3 is a step in which the number of defects on the substrate ZA to which the removal solvent has been applied is measured using a defect inspection device. Specifically, the number of defects present on the substrate ZA (preferably the number of defects with a size of 19 nm or larger) is measured. Defect inspection of substrate ZA in process ZA3 can be performed using a defect inspection device (e.g., dark-field defect inspection device: KLA-Tencor's Surfscan® SP5, etc.). By performing the above step ZA3, the number of defects present on the substrate ZA after application of the removal solvent (preferably the number of defects with a size of 19 nm or larger) (number of defects after application of the removal solvent) is measured.

[0047] ·Process Z4 Step ZA4 is a process that calculates the number of defects originating from the removal solvent (number of removal solvent defects) by subtracting the number of defects measured in step ZA1 (number of original substrate defects) from the number of defects measured in step ZA3 (number of defects after application of removal solvent). As mentioned above, the number of defects obtained by performing the above process ZA4 is 4.00 defects / cm². 2 Preferably, the following is true: 2.30 pieces / cm 2 It is more preferable that the following conditions are met: 1.50 pieces / cm 2 It is even more preferable that the following conditions be met: 0.75 pieces / cm 2 The following is particularly preferable. The lower limit is, for example, 0.00 pieces / cm². 2 That's all. As mentioned above, the number of defects larger than 19 nm obtained by performing the ZA4 process is 4.00 defects / cm². 2 Preferably, the following is true: 2.30 pieces / cm 2 It is more preferable that the following conditions are met: 1.50 pieces / cm 2 It is even more preferable that the following conditions be met: 0.75 pieces / cm 2 The following is particularly preferable. The lower limit is, for example, 0.00 pieces / cm². 2 That's all. If there are many defects originating from the removal solvent used in process X2, scattering may occur during the defect inspection of the substrate ZA performed in process X3, hindering accurate measurement of the number of defects. For this reason, it is preferable to use a highly clean removal solvent in process X2, as this improves the accuracy of the defect inspection in process X3 (and consequently, the inspection accuracy of this inspection method).

[0048] One method for improving the cleanliness of the removal solvent is filtration using a filter. There are no particular restrictions on the filter pore size and material, and they can be adjusted as appropriate according to the composition. The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with at least one different pore size and material may be used in combination. In addition, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulating filtration process. As for the filter, one that reduces elution, such as the one disclosed in Japanese Patent Application Publication No. 2016-201426, is preferred. In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon. As a metal adsorbent, for example, one disclosed in Japanese Patent Application Publication No. 2016-206500 can be cited. Furthermore, methods for removing impurities such as metals include selecting raw materials with a low metal content, performing filter filtration on the raw materials, or performing distillation under conditions that minimize contamination as much as possible, such as by lining the equipment with Teflon®. The preferred conditions for filter filtration of the raw materials are the same as those described above. To prevent contamination with impurities, the removal solvent is preferably stored in a container as described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Publication No. 2015-123351, Japanese Patent Publication No. 2017-13804, etc.

[0049] (Procedure for step X2) There are no particular limitations on the method for removing the coating formed in step X1 from the substrate X using a removal solvent. Examples of removal methods include immersing the substrate in a tank filled with a removal solvent for a certain period of time, applying the removal solvent to the substrate surface using surface tension and letting it 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 rotating at a constant speed. Removal using the above methods can be performed in an organic developing unit. Other examples of removal methods include removal using a coater cup and removal using an organic developing unit. Removal using a spin coating method with a spinner is also preferred. When performing the removal method using a spin coating method with a spinner, the rotation speed is preferably 500 to 3000 rpm. The supply flow rate of the removal solvent is preferably 0.2 to 10.0 mL / s, more preferably 0.5 to 3.0 mL / s. The supply time is preferably 3 to 300 seconds, more preferably 5 to 60 seconds.

[0050] The temperature of the removal solvent is not particularly limited, but is preferably 0 to 50°C, and more preferably 15 to 35°C. The removal time for the removal process using the removal solvent is preferably 800 seconds or less, preferably 300 seconds or less, and more preferably 60 seconds or less, in order to achieve better inspection accuracy. The lower limit is, for example, 5 seconds or more. If the removal time in process X2 is too long, not only the coating but also minute components (foreign matter) are more likely to be removed from the substrate, which may make it impossible to accurately measure the number of defects in the defect inspection in process X3. For this reason, it is preferable that the removal time used in process X1 be shorter in order to achieve better defect inspection accuracy in process X3 (and consequently, to improve the inspection accuracy of this inspection method). The removal time is calculated from the moment the removal solvent comes into contact with the coating film and can be adjusted as appropriate by the equipment used during manufacturing, such as a coater.

[0051] After the removal process, it is preferable to dry the substrate X. As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate or the like. The heating temperature is preferably 80 to 200°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, it is preferable to heat at 100°C for 60 seconds.

[0052] <Process X3> Step X3 is a step in which the number of defects on the substrate X after the coating film has been removed in step X2 is measured using a defect inspection device. Specifically, the number of defects present on the substrate X (preferably the number of defects with a size of 19 nm or larger) is measured. Defect inspection of substrate X in process X3 can be performed using a defect inspection device (e.g., dark-field defect inspection device: KLA-Tencor, Surfscan® SP5, etc.). By performing the above step X3, the number of defects present on the substrate X after removal with the removal solvent (preferably the number of defects with a size of 19 nm or larger) (Total number of defects after solvent removal treatment) is measured.

[0053] [Second embodiment of the inspection method] The second embodiment of the inspection method will be described below. A second embodiment of the inspection method is a method for inspecting a composition (inspection composition) selected from the group consisting of resist compositions and thermosetting compositions, comprising steps X1, X2, and X3 (steps X3A and X3B), and optionally step Y1. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a resist composition, this step involves removing the coating film from the substrate X using a removal solvent containing an organic solvent (removal solvent) without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without thermal curing treatment. Process X3: Process X3 includes processes X3A and X3B. Step X3A: A step in which the number of defects on the substrate X after the above coating film has been removed (i.e., after step X2) is measured using a defect inspection device. Step X3B: A step to calculate the number of defects originating from the inspection composition by subtracting the number of defects that existed on the substrate X before application to step X1 (number of defects originating from the substrate: original substrate defect count) from the number of defects measured in step X3A. However, if the number of defects originating from the substrate X (original substrate defect count) is unknown, the second embodiment of the inspection method further includes step Y1, and the number of defects measured in step Y1 is taken as the number of defects originating from the substrate X (original substrate defect count). Process Y1: A process performed before process X1, in which the number of defects on the substrate X to be used in process X1 is measured using a defect inspection device.

[0054] The second embodiment of the inspection method includes a step X3B in which step X3 subtracts the number of defects originating from the substrate X (original substrate defect count) from the number of defects measured in step X3A (total number of defects after solvent removal treatment). With this configuration, the number of defects originating from the inspection composition can be inspected with higher accuracy.

[0055] The following describes each step. <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.

[0056] <Process X3 (Process X3A and Process X3B)> Process X3 comprises processes 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 in which the number of defects originating from the inspection composition is calculated by subtracting the number of defects that existed on the substrate X before it was applied to step X1 (number of defects originating from the substrate: original substrate defect count) from the number of defects measured in step X3A. If the number of defects originating from substrate X (original substrate defect count) is already publicly known from a catalog or other source, such nominal value can be used. If the number of defects originating from substrate X is unknown, the second embodiment of the inspection method further includes step Y1, and the value measured by this step Y1 is taken as the number of defects originating from substrate X (original substrate defect count).

[0057] <Process Y1> Process Y1 is a process performed before process X1, in which the number of defects on the substrate X to be used in process X1 is measured using a defect inspection device. Step Y corresponds to the step of performing the method for measuring the number of defects in the original substrate, as described in step X1 of the first embodiment of the inspection method, and the preferred embodiment is the same.

[0058] [Third embodiment of the inspection method] The third embodiment of the inspection method will be described below. A third embodiment of the inspection method is a method for inspecting a composition (inspection composition) selected from the group consisting of resist compositions and thermosetting compositions, comprising steps X1, X2, and X3 (steps X3A and X3C), and optionally step ZX. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a resist composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without thermal curing treatment. Process X3: Process X3 includes processes X3A and X3C. Step X3A: A step in which the number of defects on the substrate X after the above coating film has been removed (i.e., after step X2) is measured using a defect inspection device. Step X3C: A step to calculate the number of defects originating from the inspection composition by subtracting the number of defects originating from the removal solvent (number of removal solvent defects) from the number of defects measured in step X3A. However, if the number of defects originating from the removal solvent (number of removal solvent defects) is unknown, the third embodiment of the inspection method further includes step ZX, and the number of defects measured in step ZX is taken as the number of defects originating from the removal solvent (number of removal solvent defects). Process ZX: A process that carries out processes Z1 to Z4 as shown below (processes Z1 to Z4 are carried out in the order of process Z3, process Z1, process Z2, and process Z4). Process Z1: A process in which the removal solvent to be used in process X2 is applied to the substrate Z. Step Z2: A step in which the number of defects on substrate Z to which the removal solvent has been applied is measured using a defect inspection device. Process Z3: A process to measure the number of defects on the substrate Z used in process Z1 using a defect inspection device. Process Z4: A process to calculate the number of defects originating from the removal solvent used in process X2 by subtracting the number of defects measured in process Z3 from the number of defects measured in process Z2.

[0059] A third embodiment of the inspection method includes a step X3C in which step X3 subtracts the number of defects originating from the removal solvent (number of defects caused by the removal solvent) from the number of defects measured in step X3A (total number of defects after solvent removal treatment). With this configuration, the number of defects originating from the inspection composition can be inspected with higher accuracy.

[0060] The following describes each step. <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.

[0061] <Process X3 (Process X3A and Process X3C)> Process X3 comprises processes X3A and 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 process that calculates the number of defects originating from the inspection composition by subtracting the number of defects originating 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 removal solvent (number of removal solvent defects) is already publicly known from a catalog or other source, such nominal value can be used. If the number of defects originating from the removal solvent (number of removal solvent defects) is unknown, the third embodiment of the inspection method further includes a step ZX, and the value measured by this step ZX is defined as the number of defects originating from the removal solvent (number of removal solvent defects).

[0062] <Process ZX (Process Z1~Process Z4)> Process ZX is a process that determines the number of defects (number of solvent-related defects) that originate from the removal solvent used in process X2. In process ZX, processes Z1, Z2, Z3, and Z4 correspond to processes ZA2, ZA3, ZA1, and ZA4 in the defect inspection R1 described in process X2 of the first embodiment of the inspection method, and the preferred embodiment is the same.

[0063] [Fourth embodiment of the inspection method] The fourth embodiment of the inspection method will be described below. A fourth embodiment of the inspection method is a method for inspecting a composition (inspection composition) selected from the group consisting of resist compositions and thermosetting compositions, comprising steps X1, X2, and X3 (steps X3A and X3D), and optionally steps Y1 and ZX. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a resist composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without thermal curing treatment. Process X3: Process X3 includes processes X3A and X3D. Step X3A: A step in which the number of defects on the substrate X after the above coating film has been removed (i.e., after step X2) is measured using a defect inspection device. Process X3D: A process to calculate the number of defects originating from the inspection composition (number of composition defects) by subtracting the number of defects that existed on the substrate X before application to process X1 (number of defects originating from the substrate: original substrate defects) and the number of defects originating from the removal solvent (number of removal solvent defects) from the number of defects measured in process X3A. However, if the number of defects originating from the substrate X (number of original substrate defects) is unknown, the fourth embodiment of the inspection method further includes process Y1, and the number of defects measured in process Y1 is taken as the number of defects originating from the substrate (number of original substrate defects). Also, if the number of defects originating from the removal solvent (number of removal solvent defects) is unknown, the fourth embodiment of the inspection method further includes process ZX, and the number of defects measured in process ZX is taken as the number of defects originating from the removal solvent (number of removal solvent defects). Step Y1: A step performed before step X1 above, in which the number of defects on the substrate X to be used in step X1 is measured using a defect inspection device. Process ZX: A process that is performed before the above-mentioned process X2, comprising processes Z1 to Z4 (processes Z1 to Z4 are performed in the order of process Z3, process Z1, process Z2, and process Z4). Process Z1: A process in which the removal solvent to be used in process X2 is applied to the substrate Z. Step Z2: A step in which the number of defects on substrate Z to which the removal solvent has been applied is measured using a defect inspection device. Process Z3: A process to measure the number of defects on the substrate Z used in process Z1 using a defect inspection device. Process Z4: A process to calculate the number of defects originating from the removal solvent used in process X2 by subtracting the number of defects measured in process Z3 from the number of defects measured in process Z2.

[0064] The fourth embodiment of the inspection method includes a step X3D in which, in step X3, the number of defects originating from the substrate X (original substrate defects) and the number of defects originating from the removal solvent (removed solvent defects) are subtracted from the number of defects measured in step X3A (total number of defects after solvent removal treatment). With the above configuration, the number of defects originating from the inspection composition (composition defects) can be inspected with higher accuracy.

[0065] The following describes each step. <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 X3D)> Process X3 comprises processes 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 in which the number of defects originating from the inspection composition (number of composition defects) is calculated by subtracting the number of defects that existed on the substrate X before application to step X1 (number of defects originating from the substrate X: original substrate defects) and the number of defects originating 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 substrate X (original substrate defect count) is already publicly known from a catalog or other source, such nominal value can be used. If the number of defects originating from substrate X is unknown, the fourth embodiment of the inspection method further includes step Y1, and the value measured by this step Y1 is taken as the number of defects originating from substrate X (original substrate defect count). Furthermore, if the number of defects originating from the removal solvent (number of removal solvent defects) is already publicly known from a catalog or other source, such nominal value can be used. If the number of defects originating from the removal solvent (number of removal solvent defects) is unknown, the fourth embodiment of the inspection method further includes a step ZX, and the value measured by step ZX is defined as the number of defects originating from the removal solvent (number of removal solvent defects).

[0067] <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.

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

[0069] [Fifth embodiment of the inspection method] A fifth embodiment of the inspection method is a method for inspecting a composition (inspection composition) selected from the group consisting of resist compositions and thermosetting compositions, and comprises the following steps X1, X2, X3 (steps X3A and X3E), Y1, and ZX. Step X1: A step in which the inspection composition is applied to the substrate X to form a coating film. Step X2: If the inspection composition is a resist composition, this step involves removing the coating film from the substrate using a removal solvent containing an organic solvent (removal solvent) without exposure by irradiation with active light or radiation; if the inspection composition is a thermosetting composition, this step involves removing the coating film from the substrate X using a removal solvent containing an organic solvent (removal solvent) without thermal curing treatment. Step X3A: A step in which the number of defects on the substrate X after the above coating film has been removed is measured using a defect inspection device. Process Y1: A process performed before process X1 above, in which the number of defects on the substrate X to be used in process X1 is measured using a defect inspection device. Process ZX: A process that is performed before the above-mentioned process X2, and comprises processes Z1 to Z4 (processes Z1 to Z4 are performed in the order of process Z3, process Z1, process Z2, and process Z4). Process Z1: A process in which the removal solvent to be used in process X2 is applied to the substrate Z. Step Z2: A step in which the number of defects on substrate Z to which the removal solvent has been applied is measured using a defect inspection device. Process Z3: A process to measure the number of defects on the substrate Z used in process Z1 using a defect inspection device. Process Z4: A process to calculate the number of defects originating from the removal solvent used in process X2 by subtracting the number of defects measured in process Z3 from the number of defects measured in process Z2. Step 3E: A step to calculate the number of defects originating from the inspection 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.

[0070] The following describes each step.

[0071] <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.

[0072] <Process X3 (Process X3A and Process X3E)> Process X3 comprises processes 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 in which the number of defects originating from the inspection composition (number of composition defects) is calculated 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).

[0073] <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.

[0074] <Process ZX> In the fifth embodiment of the inspection method, step ZX is the same as step ZX in the third embodiment of the inspection method described above.

[0075] [Test composition] The inspection composition in the inspection method of the present invention is selected from the group consisting of resist compositions and thermosetting compositions. Examples of suitable resist compositions and thermosetting compositions for use as inspection compositions are described below.

[0076] <<Resist Composition>> The resist composition is not particularly limited as long as the coating of the resist composition can be removed with a removal solvent, and known resist compositions such as chemically amplified resist compositions can be used. Below, an example of a resist composition suitable as a test composition will be described.

[0077] <Resist Composition (CR)> The resist composition is preferably a composition (hereinafter also referred to as "composition (CR)") that contains a resin whose polarity increases with the action of an acid, a photoacid generator, and a solvent. The composition (CR) will be described below.

[0078] (Resin whose polarity increases due to the action of acid) <Repeating unit with acid-degradable group (Aa)> The resin whose polarity increases due to the action of an acid (hereinafter also simply referred to as "resin (A)") preferably has a repeating unit (Aa) having an acid-degradable group (hereinafter also simply referred to as "repeating unit (Aa)"). An acid-degradable group is a group that decomposes upon the action of an acid, producing a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group that is released upon the action of an acid. In other words, resin (A) has repeating units (Aa) that decompose upon the action of an acid, producing a polar group. Resins having these repeating units (Aa) become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents.

[0079] Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0080] Examples of leaving groups that are removed by the action of an acid include the groups represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0081] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may combine to form a monocycle or polycycle. Preferred alkyl groups for Rx1 to Rx3 are C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Preferred cycloalkyl groups for Rx1 to Rx3 are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. If the resist composition is, for example, an EUV lithography resist composition, it is preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0082] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with heteroatoms such as oxygen atoms and / or groups having heteroatoms such as carbonyl groups. Furthermore, in the repeating unit having an acid-degradable group, as described later, R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the resist composition is, for example, an EUV lithography resist composition, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0083] For formula (Y3), a group represented by the following formula (Y3-1) is preferred.

[0084] [ka]

[0085] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of refining the pattern, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl or adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy of the resin (A) are increased in the repeating units having acid-degradable groups, as described later, thus ensuring film strength and suppressing clouding.

[0086] If the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms (that is, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group). Furthermore, if the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and the groups which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom which may contain a heteroatom.

[0087] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group. If the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have fluorine and iodine atoms as substituents.

[0088] In terms of further improving acid decomposition properties, when a non-aromatic ring is directly bonded to a polar group (or its residue) in a leaving group that protects a polar group, it is also preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0089] Other leaving groups that are removed by the action of an acid may include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0090] As the repeating unit (Aa), the repeating unit represented by formula (A) is also preferred.

[0091] [ka]

[0092] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. In addition, one preferred embodiment of the repeating unit represented by formula (A) is one in which at least one of L1, R1, and R2 is a fluorine atom or an iodine atom. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups which may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, L1 is preferably -CO-, an arylene group, or an arylene group-which may have a fluorine atom or an iodine atom-, and more preferably -CO-, an arylene group, or an arylene group-which may have a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. When the alkylene group has a fluorine atom or an iodine atom, the total number of fluorine atoms and iodine atoms contained in the alkylene group is not particularly limited, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0093] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0094] R2 represents a leaving group that is removed by the action of an acid and may have a fluorine atom or an iodine atom. Examples of leaving groups that may have a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that have a fluorine atom or an iodine atom, and the preferred embodiment is the same.

[0095] As the repeating unit (Aa), the repeating unit represented by the general formula (AI) is also preferred.

[0096] [ka]

[0097] In the general formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have substituents. T represents a single bond or a divalent linking group. Each of Rx1 to Rx3 independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an alkenyl group. However, if all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may bond together to form a cycloalkyl group (monocyclic or polycyclic).

[0098] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0099] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0100] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, and also preferably a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. Examples of alkenyl groups in Rx1 to Rx3 include vinyl groups. Examples of aryl groups Rx1 to Rx3 include phenyl groups. The repeating unit represented by the general formula (AI) is preferably configured such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded together to form the cycloalkyl group described above.

[0101] When each of the above groups has substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0102] The repeating unit represented by the general formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0103] The resin (A) may have one repeating unit (Aa) alone, or it may have two or more repeating units. The content of repeating units (Aa) (total content if two or more types of repeating units (Aa) are present) is preferably 15 to 80 mol%, and more preferably 20 to 70 mol%, relative to the total number of repeating units in the resin (A).

[0104] The resin (A) preferably has at least one repeating unit (Aa) selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII).

[0105] [ka]

[0106] In the general formula (A-VIII), R5 represents a tert-butyl group or a -CO-O-(tert-butyl) group. In general formula (A-IX), R6 and R7 each independently represent a monovalent organic group. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. In the general formula (AX), p represents either 1 or 2. In the general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms. In general formula (A-XII), R 10 This represents an alkyl group or adamantyl group having 1 to 3 carbon atoms.

[0107] ≪Repeating unit with acid group (A-1)≫ The resin (A) may have repeating units (A-1) having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, resulting in superior pattern shape and resolution. Preferred acid groups include, for example, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The -C(CF3)(OH)-CF2- formed in this way is also preferred as an acid group. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acid group (A-1) is preferably a repeating unit having a structure in which a polar group is protected by a leaving group that is removed by the action of the acid described above, and is different from the repeating unit having a lactone group, sultone group, or carbonate group (A-2) described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0108] As a repeating unit having an acid group, for example, a repeating unit having a phenolic hydroxyl group as described in paragraphs 0089 to 0100 of Japanese Patent Publication No. 2018-189758 can be suitably used.

[0109] When resin (A) contains repeating units (A-1) having acidic groups, the composition (CR) containing resin (A) is preferred for KrF exposure, EB exposure, or EUV exposure. In such embodiments, the content of repeating units having acidic groups in resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%, relative to the total repeating units in resin (A).

[0110] ≪A repeating unit (A-2) having at least one selected from the group consisting of lactone structure, sultone structure, carbonate structure, and hydroxyadamantane structure≫ The resin (A) may have repeating units (A-2) having at least one selected from the group consisting of lactone structures, carbonate structures, sultone structures, and hydroxyadamantane structures.

[0111] The lactone structure or sultone structure in the repeating unit having a lactone structure or sultone structure is not particularly limited, but a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure is preferred, and it is more preferred that other ring structures are fused to the 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or that other ring structures are fused to the 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure. Examples of repeating units having a lactone or sultone structure include the repeating units described in paragraphs 0094 to 0107 of WO2016 / 136354.

[0112] The resin (A) may have repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure. Examples of repeating units having a carbonate structure include the repeating units described in paragraphs 0106-0108 of WO2019 / 054311.

[0113] The resin (A) may have repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include the repeating unit represented by the following general formula (AIIa).

[0114] [ka]

[0115] In general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. However, at least one of R2c to R4c represents a hydroxyl group. Preferably, one or two of R2c to R4c are hydroxyl groups and the rest are hydrogen atoms.

[0116] ≪Repeating units containing fluorine or iodine atoms≫ The resin (A) may have repeating units having fluorine atoms or iodine atoms. Examples of repeating units having fluorine atoms or iodine atoms include the repeating units described in paragraphs 0080 to 0081 of Japanese Patent Application Publication No. 2019-045864.

[0117] ≪Repeating units with photoacid-generating groups≫ The resin (A) may also have repeating units other than those described above, which have groups that generate acid upon irradiation with radiation. Examples of repeating units having fluorine atoms or iodine atoms include the repeating units described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2019-045864.

[0118] <<Repeating units with alkali-soluble groups>> The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups with an electron-withdrawing group substituted at the α-position (e.g., hexafluoroisopropanol group), with carboxyl groups being preferred. The presence of repeating units with alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups include repeating units in which alkali-soluble groups are directly bonded to the main chain of the resin, such as repeating units made of acrylic acid and methacrylic acid, or repeating units in which alkali-soluble groups are bonded to the main chain of the resin via a linking group. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. As repeating units having alkali-soluble groups, repeating units made of acrylic acid or methacrylic acid are preferred.

[0119] ≪Repeating units that do not possess either an acid-degradable group or a polar group≫ The resin (A) may further have repeating units that do not have either an acid-degradable group or a polar group. The repeating units that do not have either an acid-degradable group or a polar group preferably have an alicyclic hydrocarbon structure.

[0120] Examples of repeating units that do not have either an acid-degradable group or a polar group include the repeating units described in paragraphs 0236-0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0121] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0122] (Properties of resin (A)) Preferably, the resin (A) is composed entirely of repeating units derived from (meth)acrylate monomers. In this case, any resin can be used in which all repeating units are derived from methacrylate monomers, all repeating units are derived from acrylate monomers, or all repeating units are derived from both methacrylate monomers and acrylate monomers. Preferably, the amount of repeating units derived from acrylate monomers is 50 mol% or less of the total repeating units in resin (A).

[0123] When composition (CR) is for argon fluoride (ArF) exposure, it is preferable that the resin (A) substantially does not contain aromatic groups from the viewpoint of ArF light transmittance. More specifically, it is preferable that the repeating units having aromatic groups are 5 mol% or less of the total repeating units of resin (A), more preferably 3 mol% or less, and ideally even more preferably 0 mol%, i.e., no repeating units having aromatic groups. Furthermore, when composition (CR) is for ArF exposure, resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure, and preferably does not contain either fluorine or silicon atoms.

[0124] When composition (CR) is for krypton fluoride (KrF) exposure, EB exposure, or EUV exposure, resin (A) preferably has repeating units having aromatic hydrocarbon groups, and more preferably has repeating units having phenolic hydroxyl groups. Examples of repeating units having phenolic hydroxyl groups include the repeating units exemplified above as the repeating units having acidic groups (A-1), and repeating units derived from hydroxystyrene (meth)acrylate. Furthermore, when composition (CR) is for KrF exposure, EB exposure, or EUV exposure, it is also preferable that resin (A) has repeating units having a structure in which the hydrogen atoms of the phenolic hydroxyl group are protected by a leaving group (a group that decomposes and leaves due to the action of an acid). When composition (CR) is for KrF exposure, EB exposure, or EUV exposure, the content of repeating units having aromatic hydrocarbon groups in resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol% relative to the total repeating units in resin (A).

[0125] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). The weight-average molecular weight (Mw) of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight-average molecular weight (Mw) of resin (A) to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, as well as deterioration of developability and deterioration of film-forming ability due to increased viscosity can be prevented. The weight-average molecular weight (Mw) of resin (A) is the polystyrene equivalent value measured by the GPC method described above. The degree of dispersion (molecular weight distribution) of resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the pattern and the better the roughness.

[0126] In composition (CR), the content of resin (A) is preferably 50 to 99.9% by mass, and more preferably 60 to 99.0% by mass, based on the total solid content of composition (CR). Furthermore, resin (A) may be used alone or in combination of two or more types. In this specification, "solid content" refers to the components that can constitute a resist film, excluding the solvent. Even if the properties of the above components are liquid, they will be treated as solid content.

[0127] (Photoacid generator (P)) The composition (CR) contains a photoacid generator (P). The photoacid generator (P) is not particularly limited as long as it is a compound that generates acid upon irradiation with radiation. The photoacid generator (P) may be in the form of a low molecular weight compound, or it may be incorporated as part of a polymer. Alternatively, both the low molecular weight compound form and the polymer-integrated form may be used in combination. When the photoacid generator (P) is in the form of a low molecular weight compound, its weight-average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. If the photoacid generator (P) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). In the present invention, the photoacid generator (P) is preferably in the form of a low molecular weight compound. The photoacid generator (P) is not particularly limited as long as it is a known compound, but a compound that generates an organic acid upon irradiation with radiation is preferred, and a photoacid generator having a fluorine atom or an iodine atom in its molecule is more preferred. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0128] The volume of acid generated by the photoacid generator (P) is not particularly limited, but to suppress the diffusion of the acid generated during exposure into the unexposed areas and improve resolution, 240 Å is preferred. 3 The above is preferable, 305Å 3 The above is more preferable, 350 Å 3 The above is even more preferable, 400 Å 3 The above is particularly preferable. Furthermore, from the viewpoint of sensitivity or solubility in the coating solvent, the volume of acid generated from the photoacid generator (P) is 1500 Å. 3 The following is preferable, 1000 Å 3 The following is more preferable: 700 Å 3 The following is even more preferable. The above volume values ​​are determined using "WinMOPAC" manufactured by Fujitsu Limited. To calculate the above volume values, first, the chemical structure of the acid in each example is input, then, using this structure as the initial structure, the most stable conformation of each acid is determined by molecular force field calculation using the MM (Molecular Mechanics) 3 method, and then, by performing molecular orbital calculations using the PM (Parameterized Model number) 3 method for these most stable conformations, the "accessible volume" of each acid can be calculated.

[0129] The structure of the acid generated by the photoacid generator (P) is not particularly limited, but a strong interaction between the acid generated by the photoacid generator (P) and the resin (A) is preferable in order to suppress acid diffusion and improve resolution. From this point of view, if the acid generated by the photoacid generator (P) is an organic acid, it is preferable that it also has a polar group in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonylsulfonylimide acid groups, bissulfonylimide acid groups, and trissulfonylmethidoic acid groups. Examples of polar groups include ether groups, ester groups, amide groups, acyl groups, sulfo groups, sulfonyloxy groups, sulfonamide groups, thioether groups, thioester groups, urea groups, carbonate groups, carbamate groups, hydroxyl groups, and mercapto groups. The number of polar groups in the generated acid is not particularly limited, but it is preferably one or more, and more preferably two or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than six, and more preferably less than four.

[0130] In particular, the photoacid generator (P) is preferably a photoacid generator comprising an anionic portion and a cation portion, as this provides superior effects for the present invention. Examples of the photoacid generator (P) include the photoacid generator described in paragraphs 0144 to 0173 of Japanese Patent Application Publication No. 2019-045864.

[0131] The content of the photoacid generator (P) is not particularly limited, but in terms of superior effects of the present invention, it is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 35% by mass, relative to the total solid content of the composition (CR). The photoacid generator (P) may be used alone or in combination of two or more types. When using two or more photoacid generators (P) in combination, it is preferable that their total amount is within the above range.

[0132] (Acid diffusion control agent (Q)) The composition (CR) may contain an acid diffusion control agent (Q). The acid diffusion control agent (Q) acts as a quencher that traps the acid generated from the photoacid generator (P) during exposure, thereby suppressing the reaction of the acid-degradable resin in the unexposed areas due to excess generated acid. Examples of acid diffusion control agents (Q) that can be used include basic compounds (DA), basic compounds whose basicity decreases or disappears upon irradiation with radiation (DB), onium salts (DC) that are relatively weak acids to the photoacid generator (P), low molecular weight compounds (DD) that have a nitrogen atom and a group that is eliminated by the action of acid, and onium salt compounds (DE) that have a nitrogen atom in the cation portion. In composition (CR), known acid diffusion control agents can be used as appropriate. For example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458 can be suitably used as acid diffusion control agents (Q).

[0133] Examples of basic compounds (DA) include the repeating units described in paragraphs 0188 to 0208 of Japanese Patent Publication No. 2019-045864.

[0134] In composition (CR), an onium salt (DC), which is a relatively weak acid relative to the photoacid generator (P), can be used as the acid diffusion control agent (Q). When a photoacid generator (P) and an onium salt that generates an acid that is relatively weaker than the acid produced by the photoacid generator (P) are mixed and used, when the acid produced by the photoacid generator (P) collides with the onium salt containing an unreacted weak acid anion due to irradiation with active light or radiation, salt exchange occurs, releasing the weak acid and producing an onium salt containing a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so the acid is seemingly deactivated and acid diffusion can be controlled.

[0135] Examples of onium salts that are relatively weak acids with respect to the photoacid generator (P) include the onium salts described in paragraphs 0226 to 0233 of Japanese Patent Application Publication No. 2019-070676.

[0136] If the composition (CR) contains an acid diffusion control agent (Q), the content of the acid diffusion control agent (Q) (total if there are multiple types) is preferably 0.1 to 10.0% by mass, and more preferably 0.1 to 5.0% by mass, relative to the total solid content of the composition (CR). In composition (CR), the acid diffusion control agent (Q) may be used alone or in combination of two or more types.

[0137] (Hydrophobic resin (E)) The composition (CR) may contain a hydrophobic resin (E) that is different from the resin (A) described above. The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups within its molecule and does not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding a hydrophobic resin (E) include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0138] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin (E) preferably has one or more of the following: "fluorine atoms," "silicon atoms," and "CH3 substructures contained in the side chain portion of the resin," and more preferably has two or more. Furthermore, the hydrophobic resin (E) preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains.

[0139] If the hydrophobic resin (E) contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chains.

[0140] When the hydrophobic resin (E) contains a fluorine atom, the fluorine atom-containing substructure is preferably an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom. A fluorine-containing alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than fluorine atoms. A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have substituents other than a fluorine atom. Examples of aryl groups having a fluorine atom include phenyl groups and naphthyl groups, in which at least one hydrogen atom of an aryl group is substituted with a fluorine atom, and they may also have substituents other than fluorine atoms. Examples of repeating units having fluorine or silicon atoms are given in paragraph 0519 of US2012 / 0251948.

[0141] Furthermore, as described above, it is also preferable that the hydrophobic resin (E) has a CH3 substructure in its side chain portion. Here, the CH3 substructures in the side chain portion of the hydrophobic resin include CH3 substructures having ethyl groups and propyl groups, etc. On the other hand, since the methyl group directly bonded to the main chain of the hydrophobic resin (E) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) has little contribution to the surface segregation of the hydrophobic resin (E) due to the influence of the main chain, it is not included in the CH3 partial structure in the present invention.

[0142] Regarding the hydrophobic resin (E), the descriptions in paragraphs

[0348] to

[0415] of JP-A-2014-010245 can be referred to, and these contents are incorporated herein.

[0143] As the hydrophobic resin (E), the resins described in JP-A-2011-248019, JP-A-2010-175859, and JP-A-2012-032544 can also be preferably used.

[0144] When the composition (CR) contains the hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition (CR).

[0145] (Solvent (F)) The composition (CR) may contain a solvent (F). When the composition (CR) is a radiation-sensitive resin composition for EUV, the solvent (F) preferably contains at least one selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. In this case, the solvent may further contain components other than the components (M1) and (M2). When the solvent containing the component (M1) or (M2) is used in combination with the above-described resin (A), the coating property of the composition (CR) is improved and a pattern with a small number of development defects can be formed, which is preferable.

[0146] When the composition (CR) is a radiation-sensitive resin composition for ArF, examples of the solvent (F) 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 contain a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.

[0147] The content of the solvent (F) in the composition (CR) is preferably determined so that the solid content concentration is 0.5 to 40% by mass. As one aspect of the composition (CR), it is also preferable that the solid content concentration is 10% by mass or more.

[0148] (Surfactant (H)) The composition (CR) may contain a surfactant (H). By containing the surfactant (H), a pattern with excellent adhesion and fewer development defects can be formed. As the surfactant (H), fluorine-based and / or silicon-based surfactants are preferred. Examples of fluorine-based and / or silicone-based surfactants include the surfactant described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Also, F-Top EF301 or EF303 (manufactured by Shin Akita Chemical Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), SC101, SC102, SC103, SC104, SC105 or SC106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-38 Fluorocarbon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-Top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Co., Ltd.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Co., Ltd.) may also be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone-based surfactant.

[0149] Furthermore, in addition to the known surfactants described above, surfactant (H) may be synthesized using a fluoroaliphatic compound produced by telomerization (also known as the telomer method) or oligomerization (also known as the oligomer method). Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as surfactant (H). This fluoroaliphatic compound can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2002-90991. Preferably, the polymer having a fluoroaliphatic group is a copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate and / or (poly(oxyalkylene))methacrylate, which may be irregularly distributed or block copolymerized. Examples of poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutylene) groups, and may also be units having alkylenes of different chain lengths within the same chain length, such as poly(block linkage of oxyethylene, oxypropylene, and oxyethylene) or poly(block linkage of oxyethylene and oxypropylene). Furthermore, the copolymer of a monomer having a fluoroaliphatic group and (poly(oxyalkylene))acrylate (or methacrylate) may not only be a binary copolymer, but may also be a ternary or higher copolymer obtained by simultaneously copolymerizing monomers having two or more different fluoroaliphatic groups and two or more different (poly(oxyalkylene))acrylate (or methacrylate), etc. For example, commercially available surfactants include Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by DIC Corporation), and C6F. 13 Examples include copolymers of acrylate (or methacrylate) having a group and (poly(oxyalkylene))acrylate (or methacrylate), and copolymers of acrylate (or methacrylate) having a C3F7 group, (poly(oxyethylene))acrylate (or methacrylate), and (poly(oxypropylene))acrylate (or methacrylate). Alternatively, non-fluorinated and / or non-silicone surfactants as described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may be used.

[0150] These surfactants (H) may be used individually or in combination of two or more.

[0151] The surfactant (H) content is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass, relative to the total solid content of the composition (CR).

[0152] (Other additives) The composition (CR) may further contain a crosslinking agent, an alkali-soluble resin, a dissolution inhibitor, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in the developer.

[0153] <Negative type resist composition (NR)> The resist composition may be a negative-type resist composition. The negative-type resist composition is preferably a composition containing a resin having phenolic hydroxyl groups, a photoacid generator, a crosslinking agent, and a solvent (hereinafter also referred to as "negative-type resist composition (NR)"). The negative resist composition (NR) is not particularly limited, but examples include the photosensitive or radiation-sensitive resin composition disclosed in International Publication No. 2016 / 072169 and the photosensitive or radiation-sensitive resin composition disclosed in International Publication No. 2019 / 039290.

[0154] <<Thermosetting composition>> The thermosetting composition is not particularly limited as long as the coating film of the thermosetting composition can be removed with a removal solvent, and any thermosetting composition that can be used in semiconductor manufacturing can be used. Thermosetting compositions that can be used in semiconductor manufacturing include thermosetting compositions for forming BARC (anti-reflective coating), SOC (spin-of-carbon coating), SOG (spin-of-glass coating), TARC (anti-reflective coating), and immersion topcoat materials. The following describes an example of an anti-reflective coating composition (a thermosetting composition for forming an anti-reflective coating), which is one of the thermosetting compositions suitable as an inspection composition.

[0155] <Anti-reflective coating composition (HC)> (A preferred embodiment of an anti-reflective coating composition (HC)) A preferred embodiment of the anti-reflective coating composition (HC) is a composition comprising an anti-reflective coating constituent material and an organic solvent component. The film constituent material may be an organic material or an inorganic material containing silicon atoms, and mainly includes binder components such as resins and / or crosslinking agents, and light-absorbing components that absorb specific wavelengths such as ultraviolet light. Each of these components may be used as a film constituent material alone, or two or more (i.e., resin and crosslinking agent, crosslinking agent and light-absorbing component, resin and light-absorbing component, and resin, crosslinking agent and light-absorbing component) may be used as a film constituent material. In addition, the anti-reflective film composition may contain surfactants, acid compounds, acid generators, crosslinking accelerators, rheology modifiers, or adhesion aids as needed.

[0156] (Another preferred embodiment of an anti-reflective coating composition (HC)) Another preferred embodiment of the anti-reflective coating composition (HC) is, for example, a composition comprising a polyfunctional epoxy compound having multiple epoxy moieties on the side chains of a core unit and to which one or more crosslinkable chromophores are bonded, a vinyl ether crosslinking agent, and an organic solvent component. "Epoxy moiety" refers to at least one of a closed epoxide ring and an open (reacted) epoxy group, such as a reacted or unreacted glycidyl group or glycidyl ether group. Furthermore, "crosslinkable chromophore" refers to the light-attenuating portion that has crosslinkable groups in a free state (i.e., unreacted) after the chromophore has been bonded to the polyfunctional epoxy compound.

[0157] Examples of monomers that induce the core unit include tris(2,3-epoxypropyl) isocyanurate, tris(4-hydroxyphenyl)methane triglycidyl ether, trimethylopropane triglycidyl ether, poly(ethylene glycol) diglycidyl ether, bis[4-(glycidyloxy)phenyl]methane, bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, 4-hydroxybenzoic acid diglycidyl ether, glycerol diglycidyl ether, 4,4'-methylenebis(N,N-diglycidylaniline), monoaryl diglycidyl isocyanurate, tetrakis(oxyranylmethyl)benzene-1,2,4,5-tetracarboxylate, bis(2,3-epoxypropyl) terephthalate, or tris(oxyranylmethyl) Examples of polymers include those containing polyfunctional glycidyls such as (1,3-)benzene-1,2,4-tricarboxylate; 1,3-bis(2,4-bis(glycidyloxy)phenyl)adamantane, 1,3-bis(1-adamantyl)-4,6-bis(glycidyloxy)benzene, 1-(2',4'-bis(glycidyloxy)phenyl)adamantane, or 1,3-bis(4'-glycidyloxyphenyl)adamantane; poly[(phenylglycidyl ether)-co-formaldehyde], poly[(o-cresylglycidyl ether)-co-formaldehyde], poly(glycidyl methacrylate), poly(bisphenol A-co-epichlorohydrin)-glycidyl end cap, poly(styrene-co-glycidyl methacrylate), or poly(tert-butyl methacrylate-co-glycidyl methacrylate).

[0158] Examples of precursors (compounds before bonding) of the above chromophores include 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1,4-dihydroxy-2-naphthoic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, and 1,1' Examples include methylene-bis(2-hydroxy-3-naphthoic acid), 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3,5-dihydroxy-4-methylbenzoic acid, 3-hydroxy-2-anthracenecarboxylic acid, 1-hydroxy-2-anthracenecarboxylic acid, 3-hydroxy-4-methoxymandelic acid, gallic acid, or 4-hydroxybenzoic acid.

[0159] (Another preferred embodiment of an anti-reflective coating composition (HC)) Another preferred embodiment of the anti-reflective coating composition (HC) is a composition comprising a monomer or polymer containing an aromatic ring and a halogenated organic solvent (also simply called a halogenated organic solvent) containing one or more carbon atoms, It is also preferable that the composition contains the above-mentioned halogenated organic solvent in a concentration of 0.001 to 50 ppm by mass relative to the total mass of the composition.

[0160] In monomers or polymers containing an aromatic ring, the aromatic ring may be monocyclic or polycyclic. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of member atoms of the aromatic ring is preferably 5 to 25, and more preferably 6 to 20. In a polymer containing an aromatic ring, the number of aromatic rings in a repeating unit containing an aromatic ring, or in a monomer containing an aromatic ring, is one or more, preferably 1 to 10, and more preferably 1 to 4. Typically, polymers containing aromatic rings are polymers (resins) that have repeating units derived from monomers containing aromatic rings. In other words, the monomer containing the aromatic ring may be the monomer from which (some or all) of the repeating units of the polymer containing the aromatic ring originate. The above composition may contain only monomers containing an aromatic ring, only polymers containing an aromatic ring, or both monomers containing an aromatic ring and polymers containing an aromatic ring. The polymer containing an aromatic ring is not particularly limited as long as it has an aromatic ring. Examples thereof include novolak resins, (meth)acrylic resins, styrene resins, cellulose resins, aromatic polyester resins, aromatic polyimide resins, polybenzoxazole resins, aromatic polyamide resins, acenaphthylene resins, and isocyanuric acid resins. In addition, if possible, the polymer containing an aromatic ring may be a copolymer having a plurality of types of repeating units in the above resins (such as styrene-(meth)acrylic copolymer resin, styrene-acenaphthylene copolymer resin, etc.).

[0161] As the above aromatic polyamide resin and the above aromatic polyimide resin, for example, the resin compounds described in Patent No. 4120584, the resin compounds described in paragraphs

[0021] to

[0053] of Patent No. 4466877, and the resin compounds described in paragraphs

[0025] to

[0050] of Patent No. 4525940 can be used. In addition, as the above novolak resin, the resin compounds described in paragraphs

[0015] to

[0058] of Patent No. 5215825 and paragraphs

[0023] to

[0041] of Patent No. 5257009 can be used. As the above acenaphthylene resin, for example, the resin compounds described in paragraphs

[0032] to

[0052] of Patent No. 4666166, the resin compounds described in paragraphs

[0037] to

[0043] of Patent No. 04388429, the polymers described in paragraphs

[0026] to

[0065] of Patent No. 5040839, and the resin compounds described in paragraphs

[0015] to

[0032] of Patent No. 4892670 can be used.

[0162] It is also preferable that the monomer containing an aromatic ring and the polymer containing an aromatic ring contain a crosslinking reaction group, and it is also preferable that they contain a hydroxyl group (preferably an aromatic hydroxyl group, more preferably a phenolic hydroxyl group). Furthermore, monomers containing aromatic rings preferably also contain lactone structures. Also, polymers containing aromatic rings preferably contain repeating units containing lactone structures.

[0163] In polymers containing aromatic rings, the content of repeating units containing aromatic rings (preferably repeating units having aromatic hydroxyl groups) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 75 to 100% by mass, relative to the total repeating units of the polymer containing aromatic rings.

[0164] The weight-average molecular weight of the polymer containing the aromatic ring is preferably 250 to 30,000, and more preferably 1,000 to 7,000.

[0165] The halogenated organic solvent preferably includes one or more selected from the group consisting of, for example, methylene chloride, chloroform, trichloroethylene, o-dichlorobenzene, and benzotrifluoride.

[0166] [Applications of the composition testing method] The above inspection method can be used for quality control of manufactured compositions. For example, compositions in which the number of defects obtained by inspection using the inspection method of the present invention is below a predetermined value can be shipped as acceptable products. Furthermore, if a composition fails the inspection, the need for further purification can be detected.

[0167] [Method for testing compositions] The method for testing a composition of the present invention relates to a method for testing a composition selected from the group consisting of resist compositions and thermosetting compositions, including the inspection method of the present invention described above, and comprises a defect count acquisition step and a determination step. Defect count acquisition process: A process of acquiring the number of defects on the substrate using the inspection method of the present invention described above. Judgment process: A process of comparing the number of defects obtained above with the reference data to determine whether it is within the acceptable range. The method for preparing the above composition (test composition) and the method for testing are as previously described, and the preferred embodiment is also the same. The number of defects obtained in the defect acquisition process is, for example, the number of defects obtained in process X3 in the first embodiment of the inspection method described above, the number of defects measured in process X3C in the third embodiment of the inspection method described above, the number of defects measured in process X3D in the fourth embodiment of the inspection method described above, and the number of defects measured in process 3E in the fifth embodiment of the inspection method described above.

[0168] In the determination process, the number of defects obtained in the defect acquisition process is compared with the reference data to determine whether the amount of foreign matter in the composition (inspection composition) is within an acceptable range. The reference data is, for example, a user-pre-set reference value (e.g., upper limit) for the number of defects, based on the correlation between the expected performance and the number of defects. Based on this reference value, the system determines whether a defect is "acceptable" or "unacceptable." A preferred embodiment of a reference value based on reference data is, for example, a defect count of 0.75 per cm. 2 The following are examples of the following embodiments.

[0169] The above testing method can be used for quality control of manufactured compositions. For example, compositions in which the number of defects obtained by testing using the testing method of the present invention is below a predetermined value can be shipped as acceptable products.

[0170] [Method for producing the composition] [First embodiment of the method for manufacturing the composition] A first embodiment of the method for producing the composition of the present invention is a method for producing a composition selected from the group consisting of resist compositions and thermosetting compositions, and comprises the following composition preparation steps and inspection steps. Composition preparation step: A step of preparing a composition (test composition) selected from the group consisting of resist compositions and thermosetting compositions. Inspection process: A process in which the composition obtained by the composition preparation process (inspection composition) is subjected to inspection based on the inspection method of the present invention. The method for preparing the above composition (test composition) and the method for testing are as previously described, and the preferred embodiment is also the same.

[0171] If the inspection process detects that the number of defects originating from the composition is greater than the desired value, it is preferable to perform a further purification process on the inspected composition after the inspection process. The inspection process may be performed only once after the composition has been prepared, or it may be performed multiple times.

[0172] A preferred embodiment of the manufacturing method of the present invention is a manufacturing method comprising the following steps: composition preparation, inspection, purification, and re-inspection. The above manufacturing method may further include a repeating step (one or more repeating steps) as needed. Composition preparation step: A step of preparing a composition (test composition) selected from the group consisting of resist compositions and thermosetting compositions. Inspection process: A process in which the composition obtained by the composition preparation process (inspection composition) is subjected to inspection based on the inspection method of the present invention. Purification process: A process in which the composition that has undergone the defect inspection process is further purified (for example, by filtration). Re-inspection step: A step in which the composition (inspection composition) that has undergone the purification step is subjected to inspection again according to the inspection method of the present invention. Repeated step: If the number of defects originating from the composition detected in the above re-inspection step does not meet a predetermined value, the above purification step and subsequent re-inspection step are repeated.

[0173] [Second Embodiment of Method for Manufacturing the Composition] A second embodiment of the method for producing the composition of the present invention is a method for producing a composition selected from the group consisting of resist compositions and thermosetting compositions, comprising the following composition preparation steps and testing steps. Composition preparation step: A step of preparing a composition (test composition) selected from the group consisting of resist compositions and thermosetting compositions. Testing Procedure: A procedure in which the composition obtained in the composition preparation procedure (test composition) is tested according to the testing method of the present invention (testing procedure). The preparation method and testing method for the above-mentioned composition (test composition) are as previously described, and the preferred embodiment is also the same.

[0174] In the second embodiment of the manufacturing method of the present invention, a composition that is judged as "acceptable" in the testing process is produced. In other words, in the second embodiment of the manufacturing method of the present invention, a high-purity composition that is judged as "acceptable" in the testing process is obtained.

[0175] [Manufacturing methods for electronic devices] Furthermore, the present invention relates to a method for manufacturing an electronic device having a step of performing an inspection based on the inspection method of the present invention described above, and to an electronic device manufactured by this manufacturing method. One specific embodiment of the method for manufacturing an electronic device is preferably a step based on the method for manufacturing the composition of the present invention described above. The electronic device is not particularly limited and is preferably mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples]

[0176] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. Note that in the table, "Number of defects per unit area (unit: defects / cm²)" is used. 2 For the term "defect count (unit: pieces)", the value was calculated to three decimal places using "number of defects (unit: pieces)", and the value shown is the result of rounding the third decimal place.

[0177] [Preparation of the removal solvent (the removal solvent used in step X2)] [Types of removal solvents] The following organic solvents were prepared as removal solvents. nBA: Butyl acetate PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether CyHx: Cyclohexanone gBL: γ-butyrolactone MAK: Methylamyl ketone PP3 / 7: Mixed solvent of PGMEA / PGME = 30 / 70 (mass ratio)

[0178] [Filtration of the removal solvent] The filters shown below were prepared, and each removal solvent was filtered according to the information in Table 1. The filtered liquid was then filled into gallon bottles. The filtration procedure was based on the method described in paragraphs 205-208 of Japanese Patent Publication No. 2016-075920. However, only one filter stage was used. <Type of filter> A: PALL 20nm nylon filter B: PALL 2nm nylon filter C: PALL PhotoClean NTD Filter D: Entegris 50nm polyethylene filter E: Entegris 10nm polyethylene filter F: Entegris 3nm polyethylene filter G: Entegris Azora photochemical filter

[0179] [Defect inspection of wafers for testing] Using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor), defect inspection was performed on a 12-inch (300 mm diameter) silicon wafer used for inspection, and the number of defects larger than 19 nm on the surface of the silicon wafer was measured. The results are shown in Table 1 as "EX: Number of defects in the original substrate".

[0180] Furthermore, in measuring the number of defects larger than 19 nm on the surface of a 12-inch silicon wafer using the dark-field defect inspection apparatus described above, the inspection area is the concentric circles of the 12-inch silicon wafer, with an area of ​​660 cm². 2This was defined as the region within the circle. In other words, it was a circle with the same center as the 12-inch silicon wafer, and with an area of ​​660 cm². 2 The area inside the circle was designated as the inspection area. Furthermore, in the tables described later, the number of defects with a size of 19 nm or larger present on the surface of a 12-inch silicon wafer using the dark-field defect inspection apparatus described above is shown as the number of defects in the circular area (unit: defects) and the number of defects per unit area (unit: defects / cm²). 2 This indicates that...

[0181] [Evaluation of the cleanliness of the removal solvent (measurement of the number of defects originating from the removal solvent used in process X2)] The filtered removal solvents described above were each connected to the resist lines of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) (note that no filters were connected to the connection piping during the connection; instead, dummy capsules were used). Subsequently, the removal solvents connected in the manner described above were applied to a 12-inch (300 mm diameter) silicon wafer, whose defect count had been previously checked in the above-described [Wafer Defect Inspection], using the coater (discharged at a flow rate of 1 mL / S for 10 seconds), and then baked at 100°C for 60 seconds. The number of defects (defect count) present on the silicon wafer surface, after coating with the removal solvent obtained by the above procedure, was measured using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5). The results are shown in Table 1 as "F: Number of defects after coating with removal solvent". Next, based on the results of "EX: Number of defects in the original substrate" and "F: Number of defects after application of the removal solvent" obtained from the above various inspections, "C: Number of defects in the removal solvent" was calculated using the following formula. The results are shown in Table 1. Formula (A1): [C: Number of defects in the removal solvent] = [F: Number of defects after application of the removal solvent] - [EX: Number of defects in the original substrate]

[0182] Table 1 is shown below. In Table 1, samples obtained using different filtration methods, even if they contain the same solvent, are indicated with the descriptive letters -A, -B, and -C. For example, "nBA-A" and "nBA-B" are both butyl acetate (nBA), but were obtained using different filtration methods. Here, "nBA-A" means that nBA was filtered using the filter C listed in the "Filter" column (i.e., "C: PALL Photoclean NTD filter" listed in <Filter Type> above). Furthermore, the notation for each removal solvent in Table 1 above will be the same as the notation in Table 1 in Tables 2 and beyond.

[0183] [Table 1]

[0184] [Preparation of resist composition (for ArF)] As a resist composition, resist composition ArF-1 was prepared by the following procedure. Furthermore, as will be shown later, three different resist compositions, ArF-1A, ArF-1B, and ArF-1C, were prepared by subjecting the resist composition ArF-1, prepared according to the procedure described below, to three different filtration treatments.

[0185] [Preparation of resist composition ArF-1] <Synthesis Example (Synthesis of Resin A-1)> 102.3 parts by mass of cyclohexanone was heated to 80°C under a nitrogen stream. While stirring this liquid, a mixed solution consisting of 22.2 parts by mass of monomer represented by structural formula M-1, 22.8 parts by mass of monomer represented by structural formula M-2, 6.6 parts by mass of monomer represented by structural formula M-3, 189.9 parts by mass of cyclohexanone, and 2.40 parts by mass of dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 5 hours. After the addition was complete, the mixture was stirred for a further 2 hours at 80°C. After the reaction solution was allowed to cool, it was reprecipitated with a large amount of hexane / ethyl acetate (mass ratio 9:1), filtered, and the resulting solid was vacuum-dried to obtain 41.1 parts by mass of acid-degradable resin (A-1).

[0186] [ka]

[0187] The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin, calculated from the GPC (carrier: tetrahydrofuran (THF)), was Mw = 9500, and the degree of dispersion was Mw / Mn = 1.60. 13 The composition ratio (molar ratio) measured by 13C-NMR was (structure derived from M-1) / (structure derived from M-2) / (structure derived from M-3) = 40 / 50 / 10.

[0188] <Preparation of Resist Composition ArF-1> The resist composition ArF-1 was prepared by mixing the following components. Note that the composition ratio of each repeating unit in the hydrophobic resin (P'-5) is intended to be a molar ratio. • Acid-degradable resin (resin A-1 mentioned above) 1,267g • Photoacid generator (PAG-7, shown below) 101g • Quencher (C-1 shown below) 22g • Hydrophobic resin (P'-5 shown below) 10g • PGMEA 38,600g

[0189] [ka] JPEG0007836264000009.jpg2644JPEG0007836264000010.jpg4854

[0190] <Filtration of resist solution> Furthermore, three different resist compositions, ArF-1A, ArF-1B, and ArF-1C, were prepared by subjecting the resist composition ArF-1, prepared using the above procedure, to three different filtration treatments as described below.

[0191] (Resist composition ArF-1A) 12,000 g of resist composition ArF-1 was filtered through a polyethylene filter with a pore size of 10 nm manufactured by Entegris to obtain resist composition ArF-1A.

[0192] (Resist composition ArF-1B) 12,000 g of resist composition ArF-1 was filtered through the following two-stage filter to obtain resist composition ArF-1B. Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0193] (Resist composition ArF-1C) 12,000 g of resist composition ArF-1 was subjected to 15 circulating filters using the following two-stage filter to obtain resist composition ArF-1C (Note that 15 circulating filters were defined as the number of times 15 times the input amount of 12,000 g was passed through the filter, with the flow rate being measured). Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0194] [Testing of resist compositions: Examples 1-11] [Defect inspection of wafers for testing (corresponding to process Y1)] Prior to evaluating defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) used for inspection was inspected using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Original substrate defect count").

[0195] [Formation of resist film (corresponding to step X1)] The prepared resist compositions ArF-1A to ArF-1C were each connected to the resist lines (but separate from the solvent lines) of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12). (Note that no filters were connected to the connection piping during the connection process; instead, dummy capsules were used.) Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer, which had been previously inspected for defects in the [Wafer Defect Inspection for Inspection (corresponding to process Y1)], using the coater described above. The coating was then baked at 100°C for 60 seconds to form a film. The thickness of the resist film (coating) was adjusted to 100 nm.

[0196] [Resist film removal process (corresponding to process X2)] Next, the resist film is removed from the silicon wafer with the resist film obtained by performing the above-described procedure for [Formation of the resist film (corresponding to step X1)] using a removal solvent. The removal solvent used here is the various organic solvents prepared in the above-described [Preparation of the removal solvent (removal solvent used in step X2)].

[0197] The removal was performed using a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) connected to the filtered removal solvent, using the same method as for [evaluation of the cleanliness of the removal solvent (measurement of the number of defects originating from the removal solvent used in process X2)]. Specifically, the removal solvent connected to the resist line of the coater, using the method described above, was applied to the silicon wafer with the resist film using the coater (discharged at a flow rate of 1 mL / S for 10 seconds), and then baked at 100°C for 60 seconds.

[0198] [Defect inspection of the substrate after removal (corresponding to process X3)] <[B: Calculation of the number of defects after removal]> After the resist film removal process described above, the wafer was subjected to a dark-field defect inspection using a Surfscan® SP5 (manufactured by KLA-Tencor) to measure the number of defects (defect count) present on the silicon wafer surface that were 19 nm or larger ([D: Total number of defects after solvent removal treatment]). Next, based on the results of "E: Number of defects in the original substrate" and "D: Total number of defects after solvent removal treatment" obtained from the various inspections described above, "B: Number of defects after removal" was calculated using the following formula. The results are shown in Table 2. Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate]

[0199] [Table 2]

[0200] <Evaluation of the number of resist defects (Calculation of [A: Number of resist defects])> Table 2 shows [B: Number of defects after removal], which includes the number of defects originating from the removal solvent, as this is the result after removal using the removal solvent. Therefore, the number of defects in the resist was defined as "A: Number of resist defects" by subtracting the number of defects originating from the removal solvent ([C: Number of defects from removal solvent]) from the number of defects after removal. "A: Number of resist defects" was specifically calculated using the following formula. Note that "[C: Number of removal solvent defects]" is based on the values ​​shown in Table 1. Formula (A3): [A: Number of resist defects] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent] The results are shown in Table 3.

[0201] [Inspection of the resist composition: Comparative Example 1] [Formation of resist film] The prepared resist compositions ArF-1A to ArF-1C were each connected to the resist lines of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) (Note that no filters were connected to the connection piping during the connection; instead, dummy capsules were used). Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer using the coater described above, and then baked at 100°C for 60 seconds to form a coating film. The thickness of the resist film (coating film) at this time was adjusted to 100 nm.

[0202] Defect inspection was performed on the above-mentioned wafer with the resist film using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor). As a result, since the inspection target was the resist film, defects smaller than 40 nm could not be evaluated. Instead, the number of defects larger than 40 nm on the surface and within the resist film (defect count) was measured. The results are shown in Table 3.

[0203] [Inspection of the resist composition: Comparative Example 2] The number of particles with a particle size of 0.15 μm or larger (LPCs) contained in 1 mL of each prepared resist composition ArF-1A to ArF-1C was measured using a particle counter (a microparticle measuring instrument from Rion Co., Ltd., liquid particle counter KS-41B).

[0204] [Evaluation of the accuracy of the testing method] Furthermore, the accuracy of this testing method was evaluated using the following method. It is known that the number of defects generated on the substrate due to foreign matter in the resist composition can be reduced by reducing the filter diameter or the number of cycles. Therefore, the number of potential defects is considered to decrease in the order of ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times). Accordingly, in evaluating the inspection methods of the examples and comparative examples, if the value of [A: number of resist defects] is consistent with the above order of potential defects and the difference is clear, it can be considered that even minute foreign matter in the resist composition has been evaluated. From the above perspective, the inspection results of the examples and comparative examples were evaluated based on the number of defects according to the following evaluation criteria. "A" indicates the order of quality: ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times), and the number of defects differs by more than twice between each sample. "B" indicates the order of quality: ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times). "C": The hierarchy is ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) and ArF-1C (filtered 15 times). (That is, the difference between ArF-1A, ArF-1B, and ArF-1C is clear, but the difference between ArF-1B and ArF-1C is not discernible.) "D": Does not fall under any of the above categories "A" through "C".

[0205] Table 3 is shown below. In Table 3, "19nm defect" in the "Measurement Target" column refers to defects with a size of 19nm or larger, "40nm coating defect" refers to coating defects with a size of 40nm or larger, and "0.15μmLPC" refers to LPCs with a particle size of 0.15μm or larger. Furthermore, in Table 3, the unit for the number of defects in Comparative Example 2 is "pieces / mL", while the unit for the number of defects in each example and Comparative Example 1 is "pieces / cm²". 2 It is either "" or "individual".

[0206] [Table 3]

[0207] [Discussion of Results] As previously mentioned, the number of defects generated on the substrate due to foreign matter in the resist composition is known to be reduced by reducing the filter diameter and the number of cycles. Therefore, it is considered that the number of potential defects decreases in the order of ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times). Accordingly, in evaluating the inspection methods of the examples and comparative examples, if the value of [A: number of resist defects] is consistent with the above-mentioned order of potential defects and the difference is clear, it can be considered that even minute foreign matter in the resist composition has been evaluated.

[0208] The inspection method described in the examples demonstrates that even minute foreign matter can be evaluated. In particular, in the inspection method described in the examples, the higher the cleanliness of the removal solvent used in the resist film removal process (the fewer defects originating from the removal solvent), the more the value of [A: number of resist defects] matches the ranking of potential defects described above, and the clearer the difference, indicating that even minute foreign matter in the resist composition can be evaluated (see the results of Examples 2, 6, 7, and 11 in particular).

[0209] On the other hand, in Comparative Example 1, only large defects of 40 nm or more could be evaluated, so it was not possible to evaluate the difference in the number of fine defects among the three resist compositions with different filtration methods described above. Furthermore, in Comparative Example 2 (LPC (Liquid Particle) Evaluation), only large defects of 0.15 μm (150 nm) or larger could be evaluated, making it impossible to evaluate the differences in the number of fine defects among the three resist compositions using the different filtration methods described above.

[0210] [Circuit board verification: Examples 12, 13] We used three different silicon wafers (silicon wafer-A, silicon wafer-B, and silicon wafer-C) with varying numbers of defects larger than 19 nm to verify the impact of the number of defects present on the substrate on inspection. Specifically, the inspection methods of Example 12 and Example 13 were carried out using the same method as the inspection method of Example 1 described above, except that the silicon wafer used was different. The removal solvent used in the inspection methods of Examples 12 and 13 is the same as the removal solvent used in the inspection method of Example 1.

[0211] The types of silicon wafers used in Example 1, Example 12, and Example 13, and the number of defects in the original substrate (E) are as follows. Example 1: Silicon wafer-A (The number of original substrate defects in silicon wafer-A is 0.02 to 0.03 per cm²) 2 ) Example 12: Silicon wafer-B (The number of original substrate defects in silicon wafer-B is 0.21-0.24 per cm²) 2 ) Example 13: Silicon wafer-C (The number of original substrate defects in silicon wafer-C is 0.78 to 1.02 per cm²) 2 )

[0212] Tables 4-6 below show the [A: number of resist defects], [B: number of defects after removal], [C: number of defects in the removal solvent], [D: total number of defects after solvent removal treatment], and [E: number of defects in the original substrate] obtained by the inspection methods of Examples 1, 12, and 13. Furthermore, the relationship between [A: number of resist defects], [B: number of defects after removal], [C: number of defects in the removal solvent], [D: total number of defects after solvent removal], and [E: number of defects in the original substrate] satisfies the following equations (A2) and (A3), as described above, and therefore also satisfies the following equation (A4). Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] Formula (A3): [A: Number of resist defects] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent] Formula (A4): [A: Number of resist defects] = [D: Total number of defects after solvent removal] - [E: Number of defects in the original substrate] - [C: Number of defects in the removal solvent]

[0213] [Table 4]

[0214] [Discussion of Results] In Example 12 using silicon wafer-B, a significant difference in [A: number of resist defects] was observed between ArF-1A (10nmUPE filtered) and ArF-1B (5nmN+1nmU filtered), but no significant difference was observed between ArF-1B (5nmN+1nmU filtered) and ArF-1C (filtered 15 times). Furthermore, in Example 13 using silicon wafer-C, the [A: number of resist defects] was 1.50 defects / cm² for all three samples: ArF-1A (10nmUPE filtered), ArF-1B (5nmN + 1nmU filtered), and ArF-1C (filtered 15 times). 2 In summary, the results showed less difference between the resists compared to Example 12. Based on the results above, the value of [E: Number of defects in the original substrate] of the test wafer used for inspection indicates that the number of defects larger than 19 nm is 0.75 per cm². 2 The following (preferably, 0.15 defects / cm² with a size of 19 nm or larger) 2 It was confirmed that the accuracy of the test improves when the following conditions are met.

[0215] [Verification of removal time: Examples 14-16] We conducted defect inspections while varying the removal time in the resist film removal process to verify the impact of the removal time on the inspection. Specifically, the inspection methods of Examples 14 to 16 were carried out in the same manner as the inspection method of Example 1 described above, except that the removal time in the resist film removal step was different.

[0216] The removal time (removal time for removal treatment using a removal solvent) in the resist film removal process for Example 1 and Examples 14-16 is as follows. Example 1: Removal time with removal solvent was 10 seconds Example 14: Removal time with removal solvent was 60 seconds. Example 15: Removal time with removal solvent was 300 seconds. Example 16: Removal time with removal solvent was 600 seconds.

[0217] Tables 7-10 below show the [A: number of resist defects], [B: number of defects after removal], [C: number of defects from the removal solvent], [D: total number of defects after solvent removal], and [E: number of defects from the original substrate] obtained by the inspection methods of Example 1 and Examples 14-16. Furthermore, the relationship between [A: number of resist defects], [B: number of defects after removal], [C: number of defects in the removal solvent], [D: total number of defects after solvent removal], and [E: number of defects in the original substrate] satisfies the following equations (A2) and (A3), as described above, and therefore also satisfies the following equation (A4). Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] Formula (A3): [A: Number of resist defects] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent] Formula (A4): [A: Number of resist defects] = [D: Total number of defects after solvent removal] - [E: Number of defects in the original substrate] - [C: Number of defects in the removal solvent]

[0218] [Table 5]

[0219] [Discussion of Results] As the removal time was increased from Example 1 to Example 14 to Example 15 to Example 16, no difference was observed between ArF-1A (10nmUPE filtered product), ArF-1B (5nmN + 1nmU filtered product), and ArF-1C (filtered 15 times). The results above confirm that inspection accuracy improves when the removal time in the resist film removal process is 300 seconds or less. In particular, it was confirmed that the difference in the number of defects between ArF-1A (10nmUPE filtered product) and ArF-1B (5nmN+1nmU filtered product) widens when the removal time in the resist film removal process is 60 seconds or less.

[0220] [Inspection after exposure treatment (ArF exposure and development): Comparative Example 9, Comparative Example 10] [Comparative Example 9] <Resist film formation> The prepared resist compositions ArF-1A to ArF-1C were each connected to the resist lines of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) (Note that no filters were connected to the connection piping during the connection; instead, dummy capsules were used). Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer using a coater, and then baked at 100°C for 60 seconds to form a coating film. The thickness of the resist film (coating film) at this time was adjusted to 100 nm. Next, using an ArF excimer laser immersion scanner (ASML XT1700i), the signal strength was measured in open frame at 30 mJ / cm². 2 The entire image was exposed with the specified exposure level. Subsequently, the film was heated at 100°C for 60 seconds (PEB), developed with tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsed with pure water, and then spin-dried. The resist film was completely dissolved by the above-described full-surface exposure and alkaline development process.

[0221] <Defect Inspection> After the above processing, a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor) was used to perform defect inspection on the wafer. The number of defects with a size of 19 nm or larger present on the surface and within the resist film (defect count) was measured after exposure, development, and rinsing of the resist film. The number of defects after exposure, development, and rinsing was calculated using the following formula. [B': Number of defects after exposure and development] = [D': Total number of defects after exposure and development] - [E: Original number of defects on the substrate] - [C': Number of defects after development and rinsing] Note that [C': Development + Rinse Defect Count] refers to the sum of [C: Defect Count of Removal Solvent], calculated for each of the developing solvent and rinsing solvent using the same method as described in [Evaluation of Cleanliness of Removal Solvent (Measurement of the number of defects originating from the removal solvent used in process X2)] in the [Preparation of Removal Solvent (Removal Solvent used in process X2)] section. The results are shown in Table 11.

[0222] [Comparative Example 10] <Resist film formation> The prepared resist compositions ArF-1A to ArF-1C were each connected to the resist lines of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) (Note that no filters were connected to the connection piping during the connection; instead, dummy capsules were used). Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer using the coater described above, and then baked at 100°C for 60 seconds to form a coating film. The thickness of the resist film (coating film) at this time was adjusted to 100 nm. Next, using an ArF excimer laser immersion scanner (ASML XT1700i), the signal strength was measured in open frame at 30 mJ / cm². 2 The entire surface was exposed with the specified exposure dose. After heating at 100°C for 60 seconds (PEB), it was developed with nBA-A (organic solvent-based development was performed using the removal solvent used in Example 1) for 30 seconds, and then spin-dried. In Comparative Example 10, since the entire surface was exposed and organic solvent-based development was performed, the resist film remained without dissolving in the solvent.

[0223] <Defect Inspection> After the above processing, the wafers were subjected to a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5) to inspect for defects larger than 40 nm, and the resist film was evaluated after exposure and development. As the inspection target was the resist film, defects smaller than 40 nm could not be evaluated. Instead, the number of defects larger than 40 nm on the surface and within the resist film after exposure and development was measured. The results are shown in Table 11.

[0224] Furthermore, the test results for Comparative Examples 9 and 10 were evaluated according to the following evaluation criteria. For reference, Table 11 also shows the results for Example 1. "A" indicates the order of quality: ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times), and the number of defects differs by more than twice between each sample. "B" indicates the order of quality: ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) > ArF-1C (filtered 15 times). "C": The hierarchy is ArF-1A (10nmUPE filtered) > ArF-1B (5nmN + 1nmU filtered) and ArF-1C (filtered 15 times). (That is, the difference between ArF-1A, ArF-1B, and ArF-1C is clear, but the difference between ArF-1B and ArF-1C is not discernible.) "D": Does not fall under any of the above categories "A" through "C".

[0225] Table 11 is shown below. In Table 11, "19nm defect" in the "Measurement Target" column refers to defects with a size of 19nm or larger, and "40nm defect" refers to coating defects with a size of 40nm or larger.

[0226] [Table 6]

[0227] In Comparative Examples 9 and 10, no significant difference in the number of defects due to filtration was observed.

[0228] [Preparation of resist composition (for EUV)] As a resist composition, resist composition EUV-1 was prepared by the following procedure. Furthermore, as will be shown later, three different resist compositions, EUV-1A, EUV-1B, and EUV-1C, were prepared by subjecting the resist composition EUV-1, prepared according to the procedure described below, to three different filtration treatments.

[0229] [Preparation of resist composition EUV-1] <Preparation of Resist Composition EUV-1> The resist composition EUV-1 was prepared by mixing the following components. • Acid-degradable resin (resin shown below (A-35)) 460g • Photoacid generator (PAG-37, shown below) 47g • Photoacid generator (PAG-38, shown below) 47g • Quencher (Q-4 shown below) 6g • PGMEA 27,608g PGME 11,832g

[0230] <Resin (A-35)> The resin (A-35) is shown below. Resin (A-35) was synthesized based on known techniques. The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin, determined from the GPC (carrier: tetrahydrofuran (THF)), was Mw = 8000, and the degree of dispersion was Mw / Mn = 1.60. 13 The composition ratio (molar ratio; corresponding to the repeating units shown below from left to right) measured by 13C-NMR was 30 / 50 / 20. Note that resin (A-35) is an acid-degradable resin.

[0231] [ka]

[0232] <Other ingredients> The photoacid generators (P-37, P-38) and quencher (Q-4) are shown below.

[0233] [ka] JPEG0007836264000018.jpg2837

[0234] <Filtration of resist solution> Furthermore, three types of resist compositions, EUV-1A, EUV-1B, and EUV-1C, were prepared by subjecting the resist composition EUV-1 prepared by the above procedure to three different filtration treatments as shown below.

[0235] (Resist composition EUV-1A) 12,000 g of resist composition EUV-1 was filtered through a PALL nylon filter with a pore size of 20 nm to obtain resist composition EUV-1A.

[0236] (Resist composition EUV-1B) 12,000 g of resist composition EUV-1 was filtered through the following two-stage filter to obtain resist composition EUV-1B. Stage 1: Entegris Azora photochemical filter Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0237] (Resist composition EUV-1C) 12,000 g of resist composition EUV-1 was subjected to 30 circulating filters using the following three-stage filter to obtain resist composition EUV-1C (30 circulating filters were defined as the number of times 30 times the input amount of 12,000 g was passed through the filter, with the flow rate measured). Stage 1: PALL nylon filter with a pore size of 2nm. Second stage: Entegris Azora photochemical filter Third row: Entegris product, pore size 1nm

[0238] [Inspection of resist compositions: Examples 17-23, Comparative Example 11] [Defect inspection of wafers for testing (corresponding to process Y1)] Prior to evaluating defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) used for inspection was inspected using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Original substrate defect count").

[0239] [Formation of resist film (corresponding to step X1)] The prepared resist compositions EUV-1A to EUV-1C were each connected to the resist lines (but separate from the solvent lines) of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12). (Note that no filters were connected to the connection piping during the connection process; instead, dummy capsules were used.) Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer, which had been pre-inspected for the number of defects in the aforementioned [Wafer Defect Inspection for Inspection (corresponding to process Y1)], using the coater described above. The coating was then baked at 100°C for 60 seconds to form a film. The thickness of the resist film (coating) was adjusted to 30 nm.

[0240] [Resist film removal process (corresponding to process X2)] Next, the resist film is removed from the silicon wafer with the resist film obtained by performing the above-described procedure for [Formation of the resist film (corresponding to step X1)] using a removal solvent. The removal solvent used here is the various organic solvents prepared in the above-described [Preparation of the removal solvent (removal solvent used in step X2)].

[0241] The removal was performed using a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) connected to the filtered removal solvent, using the same method as described above for [evaluation of the cleanliness of the removal solvent (measurement of the number of defects originating from the removal solvent used in process X2)]. Specifically, the removal solvent connected to the resist line of the coater, using the method described above, was applied to the silicon wafer with the resist film using the coater (discharged at a flow rate of 1 mL / S for 15 seconds), and then baked at 100°C for 60 seconds.

[0242] [Defect inspection of the substrate after removal (corresponding to process X3)] <[B: Calculation of the number of defects after removal]> After the above processing, a defect inspection was performed on the wafer using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor), and the number of defects with a size of 19 nm or larger on the surface of the silicon wafer was measured ([D: Total number of defects after solvent removal treatment]). Next, based on the results of "E: Number of defects in the original substrate" and "D: Total number of defects after solvent removal treatment" obtained from the various inspections described above, "B: Number of defects after removal" was calculated using the following formula. Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] Furthermore, [B: Number of defects after removal] includes the number of defects originating from the removal solvent, as it represents the result after removal using the removal solvent. Therefore, the number of defects in the resist was defined as the "number of resist defects" by subtracting the number of defects originating from the removal solvent ([C: Number of defects from removal solvent]) from the number of defects after removal. The number of resist defects was calculated using the following formula. Note that [C: Number of defects due to removal solvent] is based on the values ​​shown in Table 1. Formula (A3): [A: Number of resist defects] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent] The results are shown in Table 12.

[0243] [Inspection of resist composition: Comparative Example 11] Using a particle counter manufactured by Rion, the number of particles with a particle size of 0.15 μm or larger (LPCs) contained in 1 mL of each prepared resist composition EUV-1A to EUV-1C was measured.

[0244] [Evaluation of the accuracy of the testing method] Furthermore, the accuracy of this testing method was evaluated using the following method. It is known that the number of defects generated on the substrate due to foreign matter in the resist composition can be reduced by reducing the filter diameter or the number of cycles. Therefore, the number of potential defects is considered to decrease in the order of EUV-1A (20nm Nylon filtered) > EUV-1B (Azora + 1nm U filtered) > EUV-1C (filtered 30 times). Accordingly, in evaluating the inspection methods of the examples and comparative examples, if the numerical value of [number of resist defects] is consistent with the above-mentioned order of potential defects and the difference is clear, it can be considered that even minute foreign matter in the resist composition has been evaluated. Therefore, the test results of each example and comparative example were evaluated according to the following evaluation criteria. "A" indicates the order of quality: EUV-1A (20nm Nylon filtered) > EUV-1B (Azora + 1nm U filtered) > EUV-1C (filtered 30 times), and the number of defects differs by more than twice between each sample. "B" indicates the order of quality: EUV-1A (20nm Nylon filtered) > EUV-1B (Azora + 1nm U filtered) > EUV-1C (filtered 30 times). "C": The hierarchy is EUV-1A (20nm Nylon filtered) > EUV-1B (Azora + 1nm U filtered) and EUV-1C (filtered 30 times). (That is, the difference between EUV-1A, EUV-1B, and EUV-1C is clear, but the difference between EUV-1B and EUV-1C is not discernible.) "D": Does not fall under any of the above categories "A" through "C".

[0245] Table 12 is shown below. In Table 12, "19nm defect" in the "Measurement Target" column refers to defects with a size of 19nm or larger, and "0.15μmLPC" refers to LPCs with a particle size of 0.15μm or larger. Furthermore, in Table 12, the unit for the number of defects in Comparative Example 11 is "pieces / mL", while the unit for the number of defects in each example is "pieces / cm²". 2 It is either "" or "individual".

[0246] [Table 7]

[0247] [Discussion of Results] The inspection method described in the examples demonstrates that even minute foreign matter in the resist composition can be evaluated. In particular, in the inspection method described in the examples, the higher the cleanliness of the removal solvent used in the resist film removal process (the fewer defects), the more the value of [A: number of resist defects] matches the ranking of potential defects described above, and the clearer the difference, indicating that even minute foreign matter in the resist composition can be evaluated (see the results of Examples 18, 21, and 23 in particular). On the other hand, in Comparative Example 11 (LPC (liquid particle) evaluation), only large defects of 0.15 μm (150 nm) or larger could be evaluated, so the difference in the number of fine defects among the three resist compositions with different filtration methods described above could not be evaluated.

[0248] [Preparation of the resist composition (negative type resist composition)] As a resist composition, resist composition EBN-1 was prepared by the following procedure. Furthermore, as will be shown later, resist composition EBN-1A was prepared by subjecting resist composition EBN-1, which was prepared by the following procedure, to a filtration treatment.

[0249] [Preparation of resist composition EBN-1] <Preparation of Resist Composition EBN-1> The resist composition EBN-1 was prepared by mixing the following components. • Resin (the resin shown below (Poly-2)) 68.5g • Photoacid generator (A-3 shown below) 10g • Quencher (B-5 shown below) 1.5g • Crosslinking agent (CL-4 shown below) 20g PGMEA 3,120g PGME 7,800g

[0250] <Resin (Poly-2)> The resin (Poly-2) is shown below. The resin (Poly-2) was synthesized based on known techniques. The weight-average molecular weight (Mw: polystyrene equivalent) of the obtained resin, determined from the GPC (carrier: tetrahydrofuran (THF)), was Mw = 3500, and the degree of dispersion was Mw / Mn = 1.10. 13 The composition ratio (molar ratio) measured by 13C-NMR was 90 / 10.

[0251] [ka]

[0252] <Other ingredients> The following are the photoacid generator (A-3), quencher (B-5), and crosslinking agent (CL-4). In the photoacid generator (A-3), "Me" represents a methyl group.

[0253] [ka] JPEG0007836264000022.jpg4979JPEG0007836264000023.jpg5249

[0254] <Filtration of resist solution> Furthermore, the resist composition EBN-1A was prepared by performing the filtration treatment shown below on the resist composition EBN-1 prepared by the above procedure. (Resist composition EBN-1A) 4000g of resist composition EBN-1 was subjected to 15 circulating filters using the following two-stage filter to obtain resist composition EBN-1A (Note that 15 circulating filters were defined as the number of times 15 times the input amount of 4000g was passed through the filter, after measuring the flow rate). Stage 1: PALL nylon filter with a pore size of 2nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0255] [Testing of the resist composition: Example 24] [Defect inspection of wafers for testing (corresponding to process Y1)] Prior to evaluating defects in the resist film, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) used for inspection was inspected using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Original substrate defect count").

[0256] [Formation of resist film (corresponding to step X1)] The prepared resist composition EBN-1A was connected to the resist line of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) (however, this was a separate line from the solvent line). (Note that no filter was connected to the connection piping during the connection; a dummy capsule was used instead.) Next, the resist composition connected by the method described above was applied to a 12-inch (300 mm diameter) silicon wafer, which had been pre-checked for defects in the aforementioned [Wafer Defect Inspection for Inspection (corresponding to process Y1)], using the coater described above. The coating was then baked at 100°C for 60 seconds to form a film. The thickness of the resist film (coating) was adjusted to 50 nm.

[0257] [Resist film removal process (corresponding to process X2)] Next, the resist film is removed from the silicon wafer with the resist film obtained by performing the above-described procedure for [Formation of the resist film (corresponding to step X1)] using a removal solvent. The removal solvent used here is nBA-A prepared in the above-described procedure for [Preparation of the removal solvent (removal solvent used in step X2)].

[0258] The removal was performed using a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) connected to the filtered removal solvent, using the same method as described above for [evaluation of the cleanliness of the removal solvent (measurement of the number of defects originating from the removal solvent used in process X2)]. Specifically, the removal solvent connected to the resist line of the coater, using the method described above, was applied to the silicon wafer with the resist film using the coater (discharged at a flow rate of 1 mL / S for 15 seconds), and then baked at 100°C for 60 seconds.

[0259] [Defect inspection of the substrate after removal (corresponding to process X3)] <[B: Calculation of the number of defects after removal]> After the above processing, a defect inspection was performed on the wafer using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor), and the number of defects with a size of 19 nm or larger on the surface of the silicon wafer was measured ([D: Total number of defects after solvent removal treatment]). Next, based on the results of "E: Number of defects in the original substrate" and "D: Total number of defects after solvent removal treatment" obtained from the various inspections described above, "B: Number of defects after removal" was calculated using the following formula. Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] Furthermore, [B: Number of defects after removal] includes the number of defects originating from the removal solvent, as it is the result after removal using the removal solvent. Therefore, the number of defects in the resist was defined as "A: Number of resist defects" by subtracting the number of defects originating from the removal solvent ([C: Number of defects from removal solvent]) from the number of defects after removal. The number of resist defects was calculated using the following formula. Note that [C: Number of defects due to removal solvent] is based on the values ​​shown in Table 1. Formula (A3): [A: Number of resist defects] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent]

[0260] As a result, [A: Number of resist defects] is 0.31 defects / cm². 2 The results were as follows: From the results above, we confirmed that the same evaluation methods can be applied to negative-type resist compositions as to ArF / EUV resists.

[0261] [Inspection of organic film-forming composition (anti-reflective film-forming composition): Example 25] Next, the organic film-forming composition was tested. The organic film-forming composition used here was the anti-reflective film-forming composition AL412 (manufactured by Brewer Science).

[0262] [Defect inspection of wafers for testing (corresponding to process Y1)] Prior to evaluating defects in the organic anti-reflective coating, a 12-inch (300 mm diameter) silicon wafer (inspection wafer) used for inspection was inspected using a dark-field defect inspection system (KLA-Tencor, Surfscan® SP5), and the number of defects larger than 19 nm on the surface of the silicon wafer was measured ("E: Original substrate defect count").

[0263] [Formation of organic anti-reflective coating (corresponding to process X1)] The anti-reflective film-forming composition AL412 was connected to the resist line (a separate line from the solvent line) of a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12). (Note that no filter was connected to the connection piping during the connection; a dummy capsule was used instead.) Next, the anti-reflective coating composition AL412, which was connected by the method described above, was applied to a 12-inch (300 mm diameter) silicon wafer, whose number of defects had been previously inspected in the aforementioned [defect inspection of inspection wafer (corresponding to process Y1)], using the coater described above to form a coating film. The film thickness of the coating film was adjusted to 200 nm. When performing the above procedure, organic anti-reflective coatings are usually hardened by baking at 200°C for 60 seconds, but in this study, baking was not performed (because hardening the film would make it impossible to remove it with a removal solvent), and after application, only spin drying was performed.

[0264] [Removal process of organic anti-reflective coating (corresponding to process X2)] Next, the organic anti-reflective coating is removed from the silicon wafer with the organic anti-reflective coating obtained by performing the procedure described above for [Formation of Organic Anti-Reflection Coating (corresponding to Step X1)] using a removal solvent. The removal solvent used here is nBA-A prepared in the above-mentioned [Preparation of Removal Solvent (Removal Solvent Used in Step X2)].

[0265] The removal was performed using a coater (Tokyo Electron Limited, CLEAN TRACK® ACT® 12) connected to the filtered removal solvent, using the same method as described in the [evaluation of the cleanliness of the removal solvent (measurement of the number of defects originating from the removal solvent used in process X2)]. Specifically, the removal solvent connected to the resist line of the coater, using the method described above, was applied to a silicon wafer with an organic anti-reflective coating using the coater (discharged at a flow rate of 1 mL / S for 20 seconds), and then baked at 100°C for 60 seconds.

[0266] [Defect inspection of the substrate after removal (corresponding to process X3)] <[B: Calculation of the number of defects after removal]> After the above processing, a defect inspection was performed on the wafer using a dark-field defect inspection system (Surfscan® SP5, manufactured by KLA-Tencor), and the number of defects with a size of 19 nm or larger on the surface of the silicon wafer was measured ([D: Total number of defects after solvent removal treatment]). Next, based on the results of "E: Number of defects in the original substrate" and "D: Total number of defects after solvent removal treatment" obtained from the various inspections described above, "B: Number of defects after removal" was calculated using the following formula. Formula (A2): [B: Number of defects after removal] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] Furthermore, [B: Number of defects after removal] includes the number of defects originating from the removal solvent, as it represents the result after removal using the removal solvent. Therefore, as the number of defects in the organic anti-reflective coating, the value obtained by subtracting the number of defects originating from the removal solvent ([C: Number of defects from the removal solvent]) from the number of defects after removal was defined as "G: Number of defects in the organic anti-reflective coating". "G: Number of defects in the organic anti-reflective coating" was calculated using the following formula. Note that "[C: Number of defects in the removal solvent]" is based on the values ​​shown in Table 1. Formula (A4): [G: Number of defects in the organic anti-reflective coating] = [B: Number of defects after removal] - [C: Number of defects in the removal solvent]

[0267] As a result, the number of defects in the organic anti-reflective coating [G: number of defects] is 0.24 defects / cm². 2 The results were as follows: From the above results, we confirmed that the same evaluation methods used for organic film formation compositions (anti-reflective film formation compositions) can be applied to organic film formation compositions, just as they are used for ArF / EUV resists.

[0268] [Preparation of resist composition (for ArF)] [Preparation of the resist composition ArF-[N]] The following resist compositions, ArF-[N], were prepared as resist compositions. Here, [N] represents a number from 2 to 47. In other words, it is intended that resist compositions ArF-2 to ArF-47 were prepared. Furthermore, as will be shown later, three different resist compositions, ArF-[N]A, ArF-[N]B, and ArF-[N]C, were prepared by performing three different filtration treatments on the prepared resist composition ArF-[N]. Therefore, for example, if [N] is 2, it is intended that three different resist compositions, ArF-2A, ArF-2B, and ArF-2C, have been prepared by performing three different filtration processes on the resist composition ArF-2.

[0269] Tables 13 and 14 show the composition of the resist composition ArF-[N]([N]:2~47). Table 13 shows the types of components that make up the resist composition ArF-[N]([N]:2~47), and Table 14 shows the content (mass%) of each component shown in Table 13 in the composition. In Table 14, the content of components other than solvents is intended to be the content (mass%) relative to the total solid content of the composition. Also, "Solid content concentration (mass%)" in Table 14 is intended to be the content of components other than solvents relative to the total mass of the composition. Furthermore, the values ​​in the "Solvent (mass ratio)" column in Table 14 correspond to the solvents listed in the "Solvent" column of Table 13 from left to right. Furthermore, the film thickness (nm) in Table 14 represents the film thickness of the resist film (coating) formed when performing [Resist film formation (corresponding to step X1)] in the inspection of the resist composition in Examples 26 to 71 described later.

[0270] [Table 8]

[0271] [Table 9]

[0272] [Table 10]

[0273] [Table 11]

[0274] [Each component in Tables 13 and 14] The components in Tables 13 and 14 are shown below.

[0275] <Acid decomposable resin> Table 15 shows the structures of the acid-degradable resins A-2 to A-20, as shown in Tables 13 and 14.

[0276] [Table 12]

[0277] The structures of each monomer shown in Table 15 are shown below.

[0278] [ka]

[0279] [ka]

[0280] <Photoacid Generator> The structures of the photoacid generators F-1 to F-18, shown in Tables 13 and 14, are shown below.

[0281] [ka]

[0282] [ka]

[0283] <Quencher> The structures of quenchers C-2 to C-11, shown in Tables 13 and 14, are shown below.

[0284] [ka]

[0285] <Hydrophobic resin> The structures of the hydrophobic resins E-1 to E-15 shown in Tables 13 and 14 are shown below.

[0286] [Table 13]

[0287] The structures of each monomer shown in Table 16 are shown below.

[0288] [ka] JPEG0007836264000036.jpg35116

[0289] <Surfactants> The surfactants H-1 to H-5 shown in Tables 13 and 14 are listed below. H-1: Megafuck F176 (manufactured by DIC Corporation, fluorine-based surfactant) H-2: Megafac R-41 (manufactured by DIC Corporation, fluorine-based surfactant) H-3: Megafuck R08 (manufactured by DIC Corporation, containing fluorine and silicone-based surfactants) H-4: PF656 (manufactured by OMNOVA, a fluorine-based surfactant) H-5: PF6320 (manufactured by OMNOVA, fluorine-based surfactant)

[0290] <Solvent> The solvents F-1 to F-8 are shown below in Tables 13 and 14. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone

[0291] [Filtration of the resist solution] Furthermore, three types of resist compositions, ArF-[N]A, ArF-[N]B, and ArF-[N]C, were prepared by subjecting the prepared resist composition ArF-[N](N:2~47) to three different filtration treatments as described below. Specifically, ArF-2A to ArF-47A, ArF-2B to ArF-47B, and ArF-2C to ArF-47C were prepared.

[0292] (Resist composition ArF-[N]A) 12,000 g of the resist composition ArF-[N] was filtered through a polyethylene filter with a pore size of 10 nm manufactured by Entegris to obtain the resist composition ArF-[N]A.

[0293] (Resist composition ArF-[N]B) 12,000 g of the resist composition ArF-[N] was filtered through the following two-stage filter to obtain the resist composition ArF-[N]B. Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0294] (Resist composition ArF-[N]C) 12,000 g of the resist composition ArF-[N] was subjected to 15 circulating filters using the following two-stage filter to obtain the resist composition ArF-[N]C (Note that 15 circulating filters were defined as the number of times 15 times the input amount of 12,000 g was passed through the filter, with the flow rate measured). Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0295] [Testing of resist compositions: Examples 26-71] Except for changing the resist compositions ArF-1A to ArF-1C to resist compositions ArF-[N]A to ArF-[N]C, and changing the thickness of the resist film (coating) formed when performing [Resist film formation (corresponding to step X1)] to the thickness shown in Table 14 (for example, if the resist used is ArF-2, the thickness of the resist film (coating) in [Resist film formation (corresponding to step X1)] of the filtered resist compositions (ArF-2A, ArF-2B, ArF-2C) derived from ArF-2 is 120 nm), the resist compositions were inspected (Examples 26 to 71) and evaluated in the same manner as described in [Inspection of resist compositions: Examples 1 to 11] above. Table 17 shows the results for [B: Number of defects after removal], and Table 18 shows the results for [A: Number of resist defects]. The removal solvents (nBA-A, nBA-B) shown in Examples 26-71 are the same as the removal solvents (nBA-A, nBA-B) described in [Inspection of Resist Composition: Examples 1-11] above.

[0296] [Table 14]

[0297] [Table 15]

[0298] [Table 16]

[0299] [Table 17]

[0300] The results in Tables 17 and 18 clearly demonstrate that this inspection method is applicable to various resist compositions used for ArF exposure applications.

[0301] [Preparation of resist composition (for EUV)] [Preparation of the resist composition EUV-[N]] The following resist compositions EUV-[N] were prepared as resist compositions. Here, [N] represents a number from 2 to 21. In other words, it is intended that resist compositions EUV-2 to EUV-21 were prepared. Furthermore, as will be shown later, three different resist compositions, EUV-[N]A, EUV-[N]B, and EUV-[N]C, were prepared by performing three different filtration treatments on the prepared resist composition EUV-[N]. Therefore, for example, if [N] is 2, it is intended that three different resist compositions, EUV-2A, EUV-2B, and EUV-2C, have been prepared by performing three different filtration processes on the resist composition EUV-2.

[0302] Tables 19 and 20 show the composition of the resist composition EUV-[N]([N]:2~21). Table 19 shows the types of components that make up the resist composition EUV-[N]([N]:2~21), and Table 20 shows the content (mass%) of each component shown in Table 19 in the composition. In Table 20, the content of components other than solvents refers to the content (mass%) relative to the total solid content of the composition. Also, "Solid content concentration (mass%)" in Table 20 refers to the content of components other than solvents relative to the total mass of the composition. Furthermore, the values ​​in the "Solvent (mass ratio)" column in Table 20 correspond to the solvents listed in the "Solvent" column of Table 19 from left to right. In addition, the film thickness (nm) in Table 20 represents the film thickness of the resist film (coating) formed when performing [Resist film formation (corresponding to step X1)] in the inspection of the resist composition in Examples 72~91 described later.

[0303] [Table 18]

[0304] [Table 19]

[0305] [Each component in Tables 19 and 20] The components in Tables 19 and 20 are shown below.

[0306] <Acid decomposable resin> The structures of the acid-degradable resins E-2 to E-21 shown in Tables 19 and 20 are shown below. Table 21 also shows the composition ratio (mol% ratio; corresponding from left to right), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit of resins E-2 to E-21.

[0307] [ka]

[0308] [ka]

[0309] [Table 20]

[0310] <Photoacid Generator> The structures of the photoacid generators F-19 to F-38, shown in Tables 19 and 20, are shown below.

[0311] [ka]

[0312] [ka]

[0313] <Quencher> The structures of Quenchers C-12 to C-20 are shown below in Tables 19 and 20.

[0314] [ka]

[0315] <Hydrophobic resin> The structures of the hydrophobic resins shown in Tables 19 and 20 are shown in Table 16 above.

[0316] <Solvent> The solvents F-1, F-2, F-4, F-7, and F-8 shown in Tables 19 and 20 are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-4: Cyclohexanone F-7: Ethyl lactate F-8: γ-Butyrolactone

[0317] [Filtration of the resist solution] Furthermore, three types of resist compositions, EUV-[N]A, EUV-[N]B, and EUV-[N]C, were prepared by subjecting the prepared resist composition EUV-[N](N:2~21) to three different filtration treatments as described below. Specifically, EUV-2A to EUV-21A, EUV-2B to EUV-21B, and EUV-2C to EUV-21C were prepared.

[0318] (Resist composition EUV-[N]A) 12,000 g of the resist composition EUV-[N] was filtered through a PALL nylon filter with a pore size of 20 nm to obtain the resist composition EUV-[N]A.

[0319] (Resist composition EUV-[N]B) 12,000 g of resist composition EUV-[N] was filtered through the following two-stage filter to obtain resist composition EUV-[N]B. Stage 1: Entegris Azora photochemical filter Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0320] (Resist composition EUV-[N]C) 12,000 g of resist composition EUV-[N] was subjected to 30 circulating filters using the following three-stage filter to obtain resist composition EUV-[N]C. (Note that 30 circulating filters were defined as 30 times the amount of 12,000 g passed through the filter, with the flow rate measured each time.) Stage 1: PALL nylon filter with a pore size of 2nm. Second stage: Entegris Azora photochemical filter Third row: Entegris product, pore size 1nm

[0321] [Testing of resist compositions: Examples 72-91] Except for changing the resist compositions EUV-1A to EUV-1C to resist compositions EUV-[N]A to EUV-[N]C, and changing the film thickness of the resist film (coating) formed when performing [Resist film formation (corresponding to step X1)] to the film thickness shown in Table 20 (for example, if the resist used is EUV-2, the film thickness of the resist film (coating) in [Resist film formation (corresponding to step X1)] of the filtered resist compositions (EUV-2A, EUV-2B, EUV-2C) derived from EUV-2 is 50 nm), the resist compositions were inspected (Examples 72 to 91) and evaluated in the same manner as described in [Inspection of resist compositions: Examples 17 to 23] above. Table 22 shows the results for [B: Number of defects after removal], and Table 23 shows the results for [A: Number of resist defects]. The removal solvents (PGMEA-A, CyHx-A, PP3 / 7-A, nBA-A) shown in Examples 72-91 are the same as the removal solvents (PGMEA-A, CyHx-A, PP3 / 7-A, nBA-A) described in [Inspection of Resist Compositions: Examples 1-11] above.

[0322] [Table 21]

[0323] [Table 22]

[0324] The results in Tables 22 and 23 clearly demonstrate that this inspection method is applicable to various resist compositions used for EUV lithography.

Claims

1. A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, Step X1 involves applying the aforementioned composition to a substrate X to form a coating film, Step X2 involves removing the coating film from the substrate X using a removal solvent containing an organic solvent, The process includes step X3 of measuring the number of defects on the substrate X after removing the coating using a defect inspection device, The aforementioned organic solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone. The aforementioned removal solvent is such that the number of defects with a size of 19 nm or larger calculated in the defect inspection R1 below is 1.50 or less per cm². If the composition is a light-sensitive or radiation-sensitive composition, step X2 is performed when the coating film has not been exposed to light or radiation. If the composition is a thermosetting composition, step X2 is an inspection method applied when the coating film has not undergone thermosetting treatment. Defect inspection R1: Defect inspection R1 includes the following steps ZA1 to ZA4. Step ZA1: A step of measuring the number of defects on the substrate ZA that are 19 nm or larger in size using the defect inspection device. Step ZA2: Step of applying the removal solvent to the substrate ZA. Step ZA3: A step of measuring the number of defects with a size of 19 nm or larger on the substrate ZA to which the removal solvent has been applied, using the defect inspection device. Step ZA4: A step of calculating the number of defects of size 19 nm or larger that originate from the removal solvent by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3.

2. A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, Step X1 involves applying the aforementioned composition to a substrate X to form a coating film, Step X2 involves removing the coating film from the substrate X using a removal solvent containing an organic solvent, Step X3 involves measuring the number of defects on the substrate X after removing the coating using a defect inspection device. It has one of the steps selected from the group consisting of steps X3B, X3C, and X3D, If the composition is a light-sensitive or radiation-sensitive composition, step X2 is performed when the coating film has not been exposed to light or radiation. If the composition is a thermosetting composition, step X2 is an inspection method applied when the coating film has not undergone thermosetting treatment. Step 3B: A step to calculate the number of defects originating from the composition by subtracting the number of defects that existed on the substrate X before applying step X1 from the number of defects measured in step X3. Step X3C: A step to calculate the number of defects originating from the composition by subtracting the number of defects originating from the removal solvent from the number of defects measured in step X3. Step X3D: A step to calculate the number of defects originating from the composition by subtracting the number of defects that existed on the substrate X before application to step X1 and the number of defects originating from the removal solvent from the number of defects measured in step X3.

3. Furthermore, step Z1 involves applying the removal solvent to the substrate Z, The inspection method according to claim 2, further comprising step Z2 of measuring the number of defects on the substrate Z to which the removal solvent has been applied using the defect inspection device.

4. Furthermore, prior to step Z1, step Z3 is performed on the substrate Z using the defect inspection device to measure the number of defects on the substrate Z. The inspection method according to claim 3, further comprising: step Z4, which calculates the number of defects originating from the removal solvent used in step X2 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 claim 2, wherein the removal solvent used is such that the number of defects with a size of 19 nm or more calculated in the defect inspection R1 below is 1.50 or less per cm². Defect inspection R1: Defect inspection R1 includes the following steps ZA1 to ZA4. Step ZA1: A step of measuring the number of defects on the substrate ZA that are 19 nm or larger in size using the defect inspection device. Step ZA2: Step of applying the removal solvent to the substrate ZA. Step ZA3: A step of measuring the number of defects with a size of 19 nm or larger on the substrate ZA to which the removal solvent has been applied, using the defect inspection device. Step ZA4: A step to calculate the number of defects of size 19 nm or larger that originate from the removal solvent by subtracting the number of defects measured in step ZA1 from the number of defects measured in step ZA3.

6. The number of defects larger than 19 nm is 0.75 per cm. ２ The inspection method according to claim 5, which is as follows:

7. The inspection method according to any one of claims 2 to 6, wherein the organic solvent includes one or more selected from the group consisting of ester-based organic solvents, alcohol-based organic solvents, and ketone-based organic solvents.

8. The inspection method according to any one of claims 2 to 7, wherein the organic solvent comprises one or more selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, and γ-butyrolactone.

9. Furthermore, before step X1, there is step Y1, The inspection method according to any one of claims 1 to 8, wherein step Y1 is a step of measuring the number of defects on the substrate X used in step X1 using the defect inspection device.

10. The substrate X is a silicon wafer, and the number of defects measured in step Y1 is 0.75 per cm. ２ The inspection method according to claim 9, which is as follows:

11. The substrate X is a silicon wafer, and the number of defects with a size of 19 nm or larger on the substrate X, as measured in step Y1, is 0.75 per cm². ２ The inspection method according to claim 9, which is as follows:

12. The number of defects larger than 19 nm is 0.15 per cm. ２ The inspection method according to claim 11, which is as follows:

13. The inspection method according to any one of claims 1 to 12, wherein in step X2, the removal time of the removal treatment using the removal solvent is 300 seconds or less.

14. The inspection method according to claim 13, wherein the removal time is 60 seconds or less.

15. The inspection method according to any one of claims 1 to 14, wherein in step X2, the removal solvent contains two or more organic solvents.

16. A method for testing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, Step X1 involves applying the aforementioned composition to a substrate X to form a coating film, Step X2 involves removing the coating film from the substrate X using a removal solvent containing an organic solvent, Step X3A involves measuring the number of defects on the substrate X after removing the coating using the defect inspection device, Furthermore, prior to step X1, there are steps Y1 and ZX, If the composition is a light-sensitive or radiation-sensitive composition, step X2 is performed when the coating film has not been exposed to light or radiation. If the composition is a thermosetting composition, step X2 is applied when the coating film has not undergone thermosetting treatment. Step Y1 is a step of measuring the number of defects on the substrate X using the defect inspection device, The aforementioned step ZX includes step Z1 of applying the removal solvent to a substrate ZX that is prepared separately from the substrate X, Step Z2 involves measuring the number of defects on the substrate ZX to which the removal solvent has been applied using the defect inspection device. Step Z3 involves measuring the number of defects on the substrate ZX using the defect inspection device, The process includes a step Z4 which calculates the number of defects originating from the removal solvent by subtracting the number of defects measured in step Z3 from the number of defects measured in step Z2. The inspection method according to claim 2, further comprising step X3E, which calculates the number of defects originating from the composition by subtracting the number of defects measured in step Y1 and the number of defects calculated in step Z4 from the number of defects measured in step X3A.

17. A step of preparing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, A method for producing a composition, comprising the step of carrying out the inspection method described in any one of claims 1 to 16.

18. A method for producing the composition according to claim 17, wherein the composition is a photosensitive or radiation-sensitive composition.

19. A method for testing a composition, comprising the testing method described in any one of claims 1 to 15, The inspection method includes the step of obtaining the number of defects on the substrate after the coating film has been removed, A method for testing a composition, comprising the step of comparing the number of defects obtained with reference data to determine whether it is within an acceptable range.

20. A method for testing a composition, comprising the testing method described in claim 16, The inspection method includes the step of obtaining the number of defects originating from the composition, A method for testing a composition, comprising the step of comparing the number of defects obtained with reference data to determine whether it is within an acceptable range.

21. The standard value based on the aforementioned standard data is 0.75 pieces / cm ２ The method for testing the composition according to claim 19 or 20 is as follows:

22. A step of preparing a composition selected from the group consisting of photosensitive or radiation-sensitive compositions and thermosetting compositions, A method for producing a composition, comprising the step of carrying out the testing method described in any one of claims 19 to 21.

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