Method for analyzing photosensitive compositions, method for manufacturing photosensitive compositions, method for manufacturing electronic devices

Abstract

Provided are a method for analyzing a photosensitive composition, a method for manufacturing a photosensitive composition, and a method for manufacturing an electronic device, with which it is possible for a trace amount of metal atoms contained in the photosensitive composition to be easily detected. This method for analyzing a photosensitive composition includes: a step 1 for forming a coating film by applying the photosensitive composition onto a substrate; a step 2 for obtaining a substrate from which the coating film has been removed, by removing the coating film from the substrate without exposing the coating film to light; and a step 3 for obtaining a measured value by employing total reflection X-ray fluorescence analysis to measure a number of metal atoms per unit area on the substrate from which the coating film has been removed.

Description

[Technical Field]

[0001] The present invention relates to a method for analyzing a photosensitive composition, a method for producing a photosensitive composition, and a method for producing an electronic device. [Background technology]

[0002] Semiconductor devices are known to be manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a coating film (resist film) obtained using a photosensitive composition is formed on a substrate, and then a pattern is obtained by performing various treatments on the coating film, such as exposure treatment by irradiating it with light, development treatment using a developer solution, and rinsing treatment using a rinse solution as needed. Using the pattern obtained in this way as a mask, various treatments are performed to form an electronic circuit pattern. In semiconductor device fabrication processes like these, there is a need for pattern formation methods that can further suppress the occurrence of defects in order to improve the yield of the resulting semiconductor devices. This trend has become even more pronounced in recent years as the manufacturing of semiconductor devices with a node of 10 nm or less has been considered.

[0003] Incidentally, one of the causes of defects in the pattern is foreign matter contained in the photosensitive composition. For example, Patent Document 1 discloses a technique for removing foreign matter such as fine particles using a filter. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2000-005546 [Overview of the project] [Problems that the invention aims to solve]

[0005] As described above, technologies for removing foreign substances such as fine particles have been developed. Along with this, there is a demand for a measurement method that can confirm the presence or absence of metal atoms at a more trace level with respect to the measurement method for confirming the presence or absence of metal atoms. As a method for measuring metal atoms in a photosensitive composition, inductively coupled plasma mass spectrometry (ICP-MS) is known. However, with the above analysis method, it has not been possible to evaluate the presence or absence of metal atoms at the trace level that is currently required in the photosensitive composition.

[0006] Therefore, an object of the present invention is to provide an analysis method for a photosensitive composition that can easily detect trace metal atoms contained in the photosensitive composition. Another object of the present invention is also to provide a method for manufacturing a photosensitive composition and a method for manufacturing an electronic device using the above analysis method.

Means for Solving the Problems

[0007] The present inventors have found that the above problems can be solved by the following configuration.

[0008] (1) A step 1 of applying a photosensitive composition onto a substrate to form a coating film; A step 2 of removing the coating film from the substrate without exposing the coating film to obtain a substrate with the coating film removed; A method for analyzing a photosensitive composition, comprising a step 3 of measuring the number of metal atoms per unit area on the substrate with the coating film removed using total reflection X-ray fluorescence analysis to obtain a measurement value. (2) The method for analyzing a photosensitive composition according to (1), further comprising a step 4 of bringing a gas containing hydrogen fluoride gas into contact with the substrate with the coating film removed between step 2 and step 3. (3) The method for analyzing a photosensitive composition according to (1) or (2), further comprising a step 5 of scanning the substrate with the coating film removed with a solution containing hydrogen fluoride and hydrogen peroxide between step 2 and step 3 to recover the metal atoms on the substrate with the coating film removed into the solution. (4) The method for analyzing a photosensitive composition according to any one of (1) to (3), wherein in step 2, the coating film is removed using a solution. (5) A method for analyzing a photosensitive composition according to (4), wherein the solution is selected from the group consisting of an aqueous solution containing tetramethylammonium hydroxide, an ester-based organic solvent, an alcohol-based organic solvent, and a ketone-based organic solvent. (6) A method for analyzing a photosensitive composition according to (4) or (5), wherein the solution is 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. (7) A method for analyzing a photosensitive composition according to any one of (4) to (6), wherein the time for removing the coating film in step 2 is 300 seconds or less. (8) A method for analyzing the photosensitive composition described in (7), wherein the time required to remove the coating is 180 seconds or less. (9) A method for analyzing a photosensitive composition according to any one of (1) to (3), wherein in step 2, the coating film is removed using a gas. (10) A method for analyzing a photosensitive composition according to (9), wherein the gas is selected from the group consisting of fluorine-based gases, oxygen-based gases, and noble gases. (11) A method for analyzing a photosensitive composition according to (9) or (10), wherein the time for removing the coating film in step 2 is 300 seconds or less. (12) A method for analyzing a photosensitive composition according to any of (9) to (11), wherein the time required to remove the coating is 180 seconds or less. (13) A step of preparing a photosensitive composition, A method for producing a photosensitive composition, comprising the step of performing any of the analytical methods described in (1) to (12) on the prepared photosensitive composition. (14) A method for manufacturing an electronic device, comprising the step of performing an analysis method described in any of (1) to (12). [Effects of the Invention]

[0009] According to the present invention, a method for analyzing a photosensitive composition is provided that can easily detect trace amounts of metal atoms contained in the photosensitive composition. Furthermore, according to the present invention, it is possible to provide a method for producing a photosensitive composition and a method for producing an electronic device using the above-described analytical method. [Modes for carrying out the invention]

[0010] 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, "light" means active light or radiation. In this specification, "active light" or "radiation" means, for example, the emission line 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, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light such as excimer lasers, extreme ultraviolet (EUV) light, and X-rays, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. 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".

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

[0012] In this specification, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0013] 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.

[0014] The method for analyzing the photosensitive composition of the present invention comprises the following steps 1 to 3. Step 1: A step of applying (preferably coating) a photosensitive composition onto a substrate to form a coating film. Step 2: A step to remove the coating film from the substrate without exposing it to light, thereby obtaining a substrate with the coating film removed. Step 3: Using total internal reflection X-ray fluorescence analysis, measure the number of metal atoms per unit area on the substrate after the coating has been removed, and obtain the measured value.

[0015] A key feature of the above analysis method is that it uses total internal reflection X-ray fluorescence analysis to analyze metal atoms contained in the photosensitive composition on a substrate. The mechanism of action will be explained below. In the above analysis method, in step 1, a coating film is formed on the substrate using a photosensitive composition, and in the subsequent step 2, a removal process is performed to remove the coating film from the substrate. As a result of the removal process, metal impurities, including minute metal atoms contained in the coating film, may adhere to the surface of the substrate after step 2. In the analysis method of the present invention, in step 3, the metal atoms present on the surface of the substrate after step X2 are measured by total internal reflection X-ray fluorescence analysis. In other words, the analysis method of the present invention analyzes the metal atoms contained in the photosensitive composition on the substrate using total internal reflection X-ray fluorescence analysis. The following describes each step of the photosensitive composition of the present invention.

[0016] <Process 1> Step 1 is a step of applying (preferably coating) a photosensitive composition onto a substrate to form a coating film. The following describes the various materials used in Step 1 and the procedure for Step 1.

[0017] (Photosensitive composition) The photosensitive composition used in this process will be described later.

[0018] (substrate) There are no particular limitations on the type and size of the substrate, and it is preferable to use a known substrate used in the manufacture of semiconductor substrates. Examples of substrates include glass substrates, silicon substrates, and sapphire substrates, with silicon wafers being preferred. Furthermore, while the size of the circuit board can be, for example, approximately 300 mm in diameter, it is not limited to this. It is preferable that the substrate used in this process is cleaned beforehand to remove any foreign matter and defects. There are no restrictions on the size of foreign matter and defects on the substrate, but examples include those of 20 nm or larger.

[0019] (Step 1 procedure) One method for forming a coating film on a substrate using a photosensitive composition is to apply the photosensitive composition onto the substrate. Other examples of application methods include applying the coating using a coater cup and applying the coating using an alkaline developing unit. Applying the coating using a spinner is also preferable. The rotation speed when applying the coating using a spinner is preferably 500 to 3000 rpm. It is preferable to apply the photosensitive composition to the substrate and then dry the substrate. As for drying methods, for example, a method of drying by heating can be used. 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 90°C for 90 seconds.

[0020] 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 photosensitive composition. For example, if the photosensitive composition is to be used for pattern formation by EUV exposure or EB exposure, the film thickness is more preferably 10 to 100 nm. Also, for example, if the photosensitive composition is to be used for pattern formation by ArF immersion exposure, the film thickness is more preferably 15 to 90 nm.

[0021] <Process 2> Step 2 is a process of removing the coating film from the substrate without exposing it to light, thereby obtaining a substrate with the coating film removed. In this context, "not exposing the coating film" means that no exposure treatment is performed at an exposure level higher than the minimum exposure level at which a residual film (the cured film after exposure of the coating film) can be observed. In other words, no exposure treatment that exposes the coating film to form a pattern is performed in step 2.

[0022] The method for removing the coating in step 2 is not particularly limited and includes methods using a solution to remove the coating and methods using a gas to remove the coating. The following details each method.

[0023] The solution used in the method of removing a coating film using a solution is not particularly limited as long as it has the ability to dissolve the coating film. Examples of such solutions include alkaline developers (preferably aqueous solutions containing tetramethylammonium hydroxide) and organic solvents, which have excellent coating film removal properties.

[0024] Alkaline developers are typically alkaline aqueous solutions. The alkali source for the alkaline developer is not particularly limited and includes, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, and dibutyldipentylammonium hydroxide, as well as quaternary ammonium salts such as trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, and dimethylbis(2-hydroxyethyl)ammonium hydroxide; cyclic amines such as pyrrole and piperidine; and the like. As for the alkali source, quaternary ammonium salts are preferred, tetraalkylammonium hydroxide (preferably with 1 to 6 carbon atoms in the alkyl portion) is more preferred, and tetramethylammonium hydroxide is even more preferred. In the alkaline aqueous solution, the content of the alkali source is preferably, for example, 0.1 to 20% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 2.0 to 3.0% by mass, relative to the total mass of the alkaline aqueous solution. The pH of the alkaline aqueous solution is preferably 10.0 to 15.0, more preferably 11.0 to 15.0, and even more preferably 12.0 to 15.0. The alkaline aqueous solution may contain alcohols and / or surfactants.

[0025] As the alkaline developer, an aqueous solution containing tetramethylammonium hydroxide is preferred. The preferred content of tetramethylammonium hydroxide and the preferred pH range of the aqueous solution are the same as the preferred content of the alkali source in the alkaline aqueous solution and the preferred pH range of the alkaline aqueous solution described above. The above pH values ​​were obtained by measuring them at a liquid temperature of 25°C using a known pH meter.

[0026] The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the coating film. Examples of organic solvents include ester-based organic solvents, alcohol-based organic solvents, ketone-based organic solvents, hydrocarbon-based organic solvents, and amide-based organic solvents, with ester-based organic solvents, alcohol-based organic solvents, or ketone-based organic solvents being preferred. Examples of ester-based organic solvents include propylene glycol monomethyl ether acetate, butyl acetate, ethyl lactate, γ-butyrolactone, methyl acetate, ethyl acetate, propyl acetate, methyl formate, ethyl formate, propyl formate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, and ethyl acetoacetate. Examples of alcohol-based organic solvents include propylene glycol monomethyl ether, methanol, ethanol, n-propanol, isopropanol (IPA), n-butanol, sec-butanol, t-butanol, n-pentanol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of ketone-based organic solvents include cyclohexanone, methyl amyl ketone, acetone, -hexanone, 2-hexanone, 1-octanone, and 2-octanone.

[0027] Preferred solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl amyl ketone, cyclohexanone, ethyl lactate, butyl acetate, or γ-butyrolactone. The above solvent may be a mixed solvent. Preferably, the mixed solvent contains two or more solvents 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.

[0028] The method for removing the coating using a solution is not particularly limited, and methods include bringing the coating into contact with the solution. More specifically, methods include immersing a substrate with a coating in a tank filled with solution for a certain period of time, spraying the solution onto the surface of the solution, and continuously discharging the solution while scanning a discharging nozzle at a constant speed onto a substrate rotating at a constant speed.

[0029] Other preferred removal methods include a removal method using a coater cup and a removal method using a spinner for spin coating. When performing the removal method using a spinner for spin coating, the rotation speed is preferably 500 to 3000 rpm. The solution supply flow rate is preferably 0.2 to 15 mL / s, and more preferably 0.2 to 12 mL / s.

[0030] The temperature of the solution is not particularly limited, but is preferably 20 to 160°C, and more preferably 20 to 120°C. The removal time for the coating using the solution is preferably within 800 seconds, more preferably within 300 seconds, and even more preferably within 180 seconds. The lower limit is often, for example, 5 seconds or more. If the removal time in step 2 is within the above range, the coating is efficiently removed while metal atoms on the substrate are less likely to be removed, allowing for more accurate measurements in the total internal reflection X-ray fluorescence analysis in step 3. More specifically, the variation in values ​​when step 3 is performed multiple times is reduced. Furthermore, from the viewpoint of enabling more accurate measurements using total internal reflection X-ray fluorescence analysis, it is also preferable to combine a method of removing the coating film using a solution with step 5 described later.

[0031] After removing the coating using the solution, rinsing may be performed as needed. If an alkaline developer is used in step 2, it is preferable to use pure water as the rinsing solution in the rinsing process. Additionally, an appropriate amount of surfactant may be added to the rinsing solution. Furthermore, to reduce the number of defects, pure water filtered through the POU filter in the device may be used. In the rinsing process, when cleaning the substrate from which the coating has been removed using the rinsing solution containing the pure water described above, the cleaning method is not particularly limited. For example, a method in which the rinsing solution is continuously discharged onto a substrate rotating at a constant speed (rotary coating method), a method in which the substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dip method), and a method in which the rinsing solution is sprayed onto the surface of the substrate (spray method) can be applied. Among these, it is preferable to perform the cleaning process using the rotary coating method, and after cleaning, rotate the substrate at a rotational speed of 2000 to 4000 rpm to remove the rinsing solution from the substrate. Rinsing by the above method can be carried out in an alkaline developing unit.

[0032] Furthermore, if an organic solvent is used in step 2, a rinsing treatment may be performed after step 2, but from the viewpoint of throughput (productivity) and the amount of rinsing solution used, it is not necessary to perform a rinsing treatment. When an organic solvent is used in step 2, a general organic solvent-containing solution can be used as the rinsing solution. Preferably, the rinsing solution used contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Specific examples of the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents mentioned above include those described in the developing solution containing organic solvents that can be used in step 2, and butyl acetate or methyl isobutylcarbinol is particularly preferred. When an organic solvent is used in step 2, it is preferable to perform the rinsing treatment using a rinsing solution containing at least one organic solvent selected from the group consisting of ester-based solvents, alcohol-based solvents, and hydrocarbon-based solvents, and it is more preferable to perform the rinsing treatment using a rinsing solution containing an alcohol-based solvent or a hydrocarbon-based solvent.

[0033] When an organic solvent is used in step 2, the organic solvent contained in the rinsing solution is preferably a hydrocarbon solvent, and more preferably an aliphatic hydrocarbon solvent. As for the aliphatic hydrocarbon solvent, from the viewpoint of improving its effect, an aliphatic hydrocarbon solvent having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, and hexadecane, etc.) is preferred, an aliphatic hydrocarbon solvent having 8 or more carbon atoms is more preferred, and an aliphatic hydrocarbon solvent having 10 or more carbon atoms is even more preferred. The upper limit of the number of carbon atoms in the above-mentioned aliphatic hydrocarbon solvent is not particularly limited, but it is preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less. Among the above aliphatic hydrocarbon solvents, decane, undecane, or dodecane are preferred, with undecane being more preferred. The above components may be mixed in multiple quantities, or mixed with other organic solvents not listed above.

[0034] The water content in the rinse solution containing the organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0035] When an organic solvent is used in step 2, the vapor pressure of the rinsing solution is preferably 0.05 to 5 kPa or less, more preferably 0.1 to 5 kPa, and even more preferably 0.12 to 3 kPa at 20°C. Setting the vapor pressure of the rinsing solution to 0.05 to 5 kPa improves the temperature uniformity across the wafer surface.

[0036] A suitable amount of surfactant may be added to the rinsing solution containing an organic solvent.

[0037] When cleaning using a rinsing solution containing an organic solvent, the cleaning method is not particularly limited. For example, methods such as continuously discharging the rinsing solution onto a substrate rotating at a constant speed (rotary coating method), immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or spraying the rinsing solution onto the substrate surface (spray method) can be applied. Among these, it is preferable to perform the cleaning using the rotary coating method, and after cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinsing solution from the substrate. It is also preferable to include a heating step (PostBake) after the rinsing step. The heating temperature in the heating step after the rinsing step is preferably 40 to 160°C, more preferably 70 to 95°C, and the heating time is preferably 10 seconds to 3 minutes, more preferably 30 to 90 seconds.

[0038] Furthermore, after step 2 or the rinsing process, a process may be carried out to remove the solution or rinse liquid used in step 2 using a supercritical fluid.

[0039] It is preferable to dry the substrate after performing the removal process. 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 40 to 200°C, more preferably 70 to 160°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, even more preferably 30 to 600 seconds, and particularly preferably 30 to 200 seconds.

[0040] The gas used in the method of removing a coating using a gas is not particularly limited as long as it is a gas capable of removing the coating. Examples of such gases include fluorine-based gases, oxygen-based gases, and noble gases, which have excellent coating removal properties. Examples of fluorinated gases include gases in which hydrogen atoms of hydrocarbons are replaced with fluorine atoms, such as CF4 and CHF3. Examples of oxygen-based gases include oxygen (O2), carbon dioxide (CO2), and nitrogen oxide gases (N2O, NO, NO2). Examples of noble gases include helium, neon, argon, krypton, and xenon.

[0041] The method for removing a coating using a gas is not particularly limited, but dry etching is one example. In dry etching, the introduced gas collides with electrons in the plasma, generating active radicals and reactive ions that have dissociated into various forms, which causes etching. The conditions for the dry etching process are selected appropriately according to the material of the coating film. The removal time for the coating using gas is preferably within 800 seconds, more preferably within 300 seconds, and even more preferably within 180 seconds. The lower limit is often, for example, 5 seconds or more. If the removal time in step 2 is within the above range, the coating is efficiently removed while metal atoms on the substrate are less likely to be removed, allowing for more accurate measurements in the total internal reflection X-ray fluorescence analysis in step 3. More specifically, the variation in values ​​when step 3 is performed multiple times is reduced. Furthermore, from the viewpoint of enabling more accurate measurements using total internal reflection X-ray fluorescence analysis, it is also preferable to combine a method of removing the coating using gas with step 5 described later.

[0042] <Process 3> Step 3 is a step in which the number of metal atoms per unit area on the substrate from which the coating has been removed is measured using total internal reflection X-ray fluorescence analysis, and the measured value is obtained. Total Reflection X-ray Fluorescence (TXRF) is a method in which excitation X-rays (primary X-rays) are irradiated onto the surface of a sample from an excitation X-ray source at a very shallow incident angle such that total internal reflection occurs with respect to the incident light. The X-rays that are totally reflected at the surface of the sample are allowed to escape to the side of the sample, while fluorescent X-rays (secondary X-rays) excited by impurities present on the surface of the sample are detected as characteristic X-rays of those impurities by a fluorescent X-ray detector positioned opposite the sample surface.

[0043] The measurement conditions for the TXRF method are not particularly limited and can be adjusted as appropriate. The unit of the above measurements is atms / cm. 2 That is the case.

[0044] <Step 4> The method for analyzing the photosensitive composition of the present invention may further include a step 4 between step 2 and step 3, in which hydrogen fluoride gas is brought into contact with a substrate from which the coating has been removed. When this analysis method includes step 4, the morphology of metal impurities present on the substrate after the coating has been removed is homogenized, and oxide films and the like are removed from the substrate after the coating has been removed, thus improving the measurement sensitivity by the TXRF method. Generally, metal impurities containing metal atoms present on a substrate after coating removal can exist in particulate or film-like forms attached to the substrate, or bonded to atoms constituting the substrate (for example, silicide form in the case of a silicon substrate). If this analysis method includes step 4, step 4 helps to homogenize the morphology of metal impurities and also removes oxide films (SiO2) and the like that have formed on the surface of the substrate after the coating has been removed. There are no particular limitations on the method for bringing the hydrogen fluoride gas into contact with the substrate from which the coating has been removed, but one example is to hold the substrate in a hydrogen fluoride gas atmosphere. More specifically, the method described in paragraphs 0013 to 0015 of Japanese Patent Application Publication No. 2001-153768 can be applied.

[0045] <Process 5> The method for analyzing the photosensitive composition of the present invention may further include a step 5 between step 2 and step 3, in which a substrate from which the coating has been removed is scanned with a solution containing hydrogen fluoride and hydrogen peroxide, and metal atoms on the substrate from which the coating has been removed are recovered into the solution. When the above solution is scanned over a substrate from which the coating has been removed, oxide films and the like are removed from the substrate, and metal impurities containing metal atoms are detached from the substrate and incorporated into the solution. The form in which the metal impurities are incorporated into the solution is not particularly limited, but examples include dissolution, dispersion, and precipitation.

[0046] When the oxide film on the substrate from which the coating has been removed is removed by scanning the solution, the hydrophobic substrate surface is exposed, and the solution becomes easier to move across the substrate. This makes it easier to recover the solution containing metal impurities. There are no particular limitations on the recovery method, but examples include methods of collecting the solution at one or more locations on the substrate from which the coating has been removed, and methods of obtaining the solution from the substrate from which the coating has been removed. Furthermore, when the collected solution is dried, the metal impurities incorporated in the solution precipitate onto the substrate from which the coating has been removed. By analyzing the content of these precipitated metal impurities using the total internal reflection X-ray fluorescence analysis method described above, the quantity and type of metal atoms on the substrate from which the coating has been removed can be analyzed. Even if the solution is obtained from the substrate from which the coating has been removed, it can be applied to a new substrate in the same manner as described above, and the quantity and type of metal impurities on the new substrate can be analyzed using the same method. In this specification, the operation of depositing metal impurities onto a substrate from which the coating has been removed by the above-described operation is also referred to as concentration and accumulation.

[0047] <Photosensitive composition> The photosensitive composition used in the analytical method of the present invention is not particularly limited, but known photosensitive compositions can be cited. The specific embodiments of the photosensitive composition will be described in detail later, but when the presence of metal atoms is confirmed by the analysis method of the photosensitive composition described above, the photosensitive composition often contains metal impurities that include metal atoms. The type of metal atom is not particularly limited, but at least one specific atom selected from the group consisting of Fe, Cr, Ti, Ni, and Al is mentioned. The metal impurity may contain one of the above metal atoms alone, or two or more of them.

[0048] Metallic impurities only need to contain metal atoms, and their form is not particularly limited. Examples include elemental metal atoms, compounds containing metal atoms (hereinafter also referred to as "metallic compounds"), and complexes thereof.

[0049] One preferred embodiment of the photosensitive composition is a photosensitive composition containing an alkali-soluble component. Below, an example of an embodiment of a photosensitive composition containing an alkali-soluble component that is suitable as a photosensitive composition will be described.

[0050] A photosensitive composition containing an alkali-soluble component refers to a photosensitive composition in which the exposed area hardens and the unexposed area can be removed with an alkaline developer. As a photosensitive composition containing an alkali-soluble component, for example, a known negative-type photosensitive composition that can be developed with alkali can be used. In a negative-type photosensitive composition that can be developed with alkali, the exposed areas usually harden, and the unexposed areas can be removed with an alkaline developer. Furthermore, the alkali-soluble component is preferably a component that can be dissolved (including both partial and complete dissolution) in the alkaline developer used during pattern formation. A preferred embodiment of the alkali-soluble component is an alkali-soluble resin having a phenolic hydroxyl group. A phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxyl group. The aromatic ring of the above aromatic ring group may be monocyclic or polycyclic, and examples include a benzene ring and a naphthalene ring. The following describes an example of a suitable negative-type photosensitive composition.

[0051] (Preferred embodiment of negative-type photosensitive composition 1) Examples of negative-type photosensitive compositions that can be developed with alkali include compositions containing an alkali-soluble resin, a photoacid generator, a crosslinking agent, and a solvent.

[0052] The following describes a specific embodiment of Preferred Embodiment 1 of the negative-type photosensitive composition, using the negative-type photosensitive composition (R) as an example. The negative-type photosensitive composition (R) comprises an alkali-soluble resin, a photoacid generator, a crosslinking agent, and a solvent.

[0053] Alkali-soluble resins As the alkali-soluble resin, an alkali-soluble resin having a phenolic hydroxyl group (hereinafter also referred to as "resin (P)") is preferred. The definition of "phenolic hydroxyl group" is as described above.

[0054] • Repeating units having phenolic hydroxyl groups The resin (P) more preferably contains repeating units having phenolic hydroxyl groups. As a repeating unit having a phenolic hydroxyl group, for example, a repeating unit represented by the following general formula (II) is preferred.

[0055] [ka]

[0056] In the formula, R2 represents a hydrogen atom, an optionally substituted methyl group, or a halogen atom (preferably a fluorine atom). B' represents a single bond or a divalent linking group. Ar' represents an aromatic ring group. m represents an integer of 1 or more.

[0057] Examples of methyl groups that may have substituents represented by R2 include trifluoromethyl groups and hydroxymethyl groups. R2 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0058] The divalent linking group represented by B' is preferably a carbonyl group, an alkylene group (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), a sulfonyl group (-S(=O)2-), -O-, -NH-, or a divalent linking group formed by combining these. As for B', a single bond, a carbonyloxy group (-C(=O)-O-), or -C(=O)-NH- is preferred, a single bond or a carbonyloxy group (-C(=O)-O-) is more preferred, and a single bond is even more preferred.

[0059] The aromatic ring represented by Ar' may be either a monocyclic or polycyclic aromatic ring, and examples include aromatic hydrocarbon rings having 6 to 18 substituents such as benzene rings, naphthalene rings, anthracene rings, fluorene rings, and phenanthrene rings; and aromatic heterocyclic rings including heterocyclic rings such as thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. Among these, aromatic hydrocarbon rings are preferred, benzene rings or naphthalene rings are more preferred, and benzene rings are even more preferred. Furthermore, the aromatic ring represented by Ar' may have further substituents. Examples of substituents include alkyl groups, cycloalkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, alkoxycarbonyl groups, alkylcarbonyl groups, alkylcarbonyloxy groups, alkylsulfonyloxy groups, and arylcarbonyl groups.

[0060] m is preferably an integer from 1 to 5, more preferably from 1 to 3, and even more preferably 1. When m is 1 and Ar' is a benzene ring, the substitution position of -OH may be the para, meta, or ortho position relative to the bond position with B' (or the polymer backbone if B' is a single bond) of the benzene ring, but the para position is preferred.

[0061] The resin (P) may be a homopolymer composed solely of repeating units having the aforementioned phenolic hydroxyl groups, or it may contain other repeating units. When the resin (P) is a copolymer, the content of repeating units having phenolic hydroxyl groups is preferably 10 to 98 mol%, more preferably 30 to 97 mol%, and even more preferably 40 to 95 mol%, relative to the total repeating units in the resin (P).

[0062] • Repeating units containing groups having a non-acid-degradable hydrocarbon structure The resin (P) may also preferably contain repeating units that include a group having a non-acid-degradable hydrocarbon structure (hereinafter also referred to as "non-acid-degradable repeating units"). A non-acid-degradable group refers to a property where decomposition does not occur due to the acid generated by a photoacid generator. The groups having a hydrocarbon structure are intended to include at least one of linear and branched hydrocarbon groups, as well as cyclic (monocyclic and polycyclic) alicyclic hydrocarbon groups, and may be bridged. Furthermore, in the above-mentioned alicyclic hydrocarbon groups, at least a portion of the carbon atoms may be substituted with heteroatoms such as oxygen atoms and / or carbonyl carbons (=CO). Among the groups having a hydrocarbon structure, cyclic (either monocyclic or polycyclic) alicyclic hydrocarbon groups are preferred.

[0063] Examples of linear and branched hydrocarbon groups include alkyl groups having 1 to 20 carbon atoms. As the monocyclic alicyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferred. Examples of alicyclic hydrocarbons constituting polycyclic alicyclic hydrocarbon groups include alicyclic hydrocarbons having a bicyclo, tricyclo, or tetracyclo structure with 5 or more carbon atoms. Among the alicyclic hydrocarbons, polycyclic cyclo rings having 6 to 30 carbon atoms are preferred, with adamantane rings, decalin rings, norbornane rings, norbornene rings, cedrol rings, isobornane rings, bornane rings, dicyclopentane rings, α-pinene rings, tricyclodecane rings, tetracyclododecane rings, or androstane rings being more preferred, and adamantane rings being even more preferred.

[0064] Furthermore, the group having the hydrocarbon structure described above may have substituents. Examples of substituents include alkyl groups (preferably having 1 to 6 carbon atoms), cycloalkyl groups (preferably having 3 to 10 carbon atoms), aryl groups (preferably having 6 to 15 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (preferably having 1 to 6 carbon atoms), carboxyl groups, carbonyl groups, thiocarbonyl groups, alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), and groups formed by combinations of these groups (preferably having a total of 1 to 30 carbon atoms, more preferably a total of 1 to 15 carbon atoms).

[0065] Among the repeating units containing a group having a non-acid-degradable hydrocarbon structure, the repeating unit represented by the following general formula (1) is preferred.

[0066] [ka]

[0067] In the formula, R represents a hydrogen atom or a methyl group. X represents a group having a non-acid-degradable hydrocarbon structure. Ar represents an aromatic ring. L represents a single bond or a divalent linking group.

[0068] A hydrogen atom is preferred as R.

[0069] Examples of divalent linking groups represented by L include carbonyl groups, alkylene groups (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), sulfonyl groups (-S(=O)2-), -O-, -NH-, and divalent linking groups formed by combining these. A single bond is preferred for L.

[0070] Examples of aromatic rings represented by Ar include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as benzene rings, naphthalene rings, anthracene rings, fluorene rings, and phenanthrene rings; and aromatic heterocycles such as thiophene rings, furan rings, pyrrole rings, benzothiophene rings, benzofuran rings, benzopyrrole rings, triazine rings, imidazole rings, benzimidazole rings, triazole rings, thiadiazole rings, and thiazole rings. The aromatic ring represented by Ar is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. Furthermore, the aromatic ring represented by Ar may have further substituents. Examples of substituents include alkyl groups (preferably having 1 to 6 carbon atoms), cycloalkyl groups (preferably having 3 to 10 carbon atoms), aryl groups (preferably having 6 to 15 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (preferably having 1 to 6 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms).

[0071] The group having a non-acid-degradable hydrocarbon group represented by X is preferably a group represented by -Y-X2 (where Y is a divalent linking group and X2 is a group having the hydrocarbon structure described above). Examples of divalent linking groups represented by Y include carbonyl groups, thiocarbonyl groups, alkylene groups (preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms), sulfonyl groups, -COCH2-, -NH-, and divalent linking groups formed by combinations thereof (preferably having a total of 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms), with carbonyl groups being preferred.

[0072] Groups having a hydrocarbon structure represented by X2 include the hydrocarbon structures described above. Among the groups having a hydrocarbon structure represented by X2, cyclic (either monocyclic or polycyclic) alicyclic hydrocarbon groups are preferred, and adamantane groups are more preferred.

[0073] The content of repeating units containing groups having a non-acid-degradable hydrocarbon structure is preferably 1 to 40 mol%, and more preferably 2 to 30 mol%, relative to the total repeating units of the resin (P).

[0074] • Other repeating units The resin (P) may contain other repeating units. Other repeating units include, for example, the repeating units disclosed in paragraphs 0125 to 0237 of Japanese Patent Publication No. 2015-148688.

[0075] The weight-average molecular weight (Mw) of the resin (P) is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 25,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0.

[0076] The resin (P) may be used alone or in combination of two or more types. In the composition, the resin (P) content is preferably 20 to 99.5% by mass, more preferably 40 to 99% by mass, and even more preferably 55 to 98% by mass, based on the total solids.

[0077] Crosslinking agent The crosslinking agent is a compound (including the resin) having a crosslinkable group capable of crosslinking the resin, and a compound that crosslinks the resin (P) by the action of an acid is preferred. As crosslinking agents, known compounds can be used as appropriate, for example, known compounds disclosed in paragraphs

[0379] to

[0431] of U.S. Patent Application Publication 2016 / 0147154A1 and paragraphs

[0064] to

[0141] of U.S. Patent Application Publication 2016 / 0282720A1. Examples of crosslinkable groups include hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, alkoxymethyl ether groups, oxirane rings, and oxetane rings, with hydroxymethyl groups, alkoxymethyl groups, oxirane rings, or oxetane rings being preferred. The crosslinking agent is preferably a compound having two or more crosslinkable groups. The crosslinking agent is preferably a phenol derivative, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure), which has a hydroxymethyl group or an alkoxymethyl group. Crosslinking agents may be used individually or in combination of two or more types. The amount of crosslinking agent in the composition is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass, based on the total solid content of the composition.

[0078] <<Photoacid Generator>> Photoacid generators are compounds that generate acid upon irradiation with active light or radiation. Examples of photoacid generators include photoacid generator X and photoacid generator Y. The composition may contain photoacid generator X alone, or it may contain both photoacid generator X and photoacid generator Y.

[0079] • Photoacid generator X As the photoacid generator X, compounds that generate organic acids upon irradiation with active light or radiation are preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

[0080] As the photoacid generator X, known compounds that generate acid upon irradiation with active light or radiation can be appropriately selected and used individually or as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0086] to

[0094] of U.S. Patent Application Publication 2015 / 0004544A1, and paragraphs

[0323] to

[0402] of U.S. Patent Application Publication 2016 / 0237190A1 can be suitably used.

[0081] As the photoacid generator X, for example, a compound represented by the following general formula (ZI), a compound represented by the general formula (ZII), or a compound represented by the general formula (ZIII) is preferable.

[0082]

Chemical formula

[0083] In the above general formula (ZI), R 201 , R 202 and R 203 each independently represents an organic group. R 201 , R 202 and R 203 The number of carbon atoms of the organic group as is generally 1 to 30, preferably 1 to 20. Also, two of R 201 ~R 203 may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group in the ring. Examples of the group formed by bonding two of R 201 ~R 203 include an alkylene group (e.g., butylene group, pentylene group) and -CH2-CH2-O-CH2-CH2-. Z - represents an anion (a non-nucleophilic anion is preferred).

[0084] Next, the general formulas (ZII) and (ZIII) will be described. In the general formulas (ZII) and (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group. R 204 ~R 207 As the aryl group of, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. R 204 ~R 207The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of aryl group skeletons having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 ~R 207 Preferably, the alkyl and cycloalkyl groups are linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group).

[0085] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 ~R 207 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. Z - This represents an anion.

[0086] Z in general formula (ZI) - and Z in general formula (ZII) - As such, an anion represented by the following general formula (3) is preferred.

[0087] [ka]

[0088] In general formula (3), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0089] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Furthermore, perfluoroalkyl groups are preferred as the alkyl group substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0090] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If there are multiple R4 and R5, they may be the same or different. The alkyl groups represented by R4 and R5 may have substituents, and preferably have 1 to 4 carbon atoms. R4 and R5 are preferably hydrogen atoms. Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in general formula (3).

[0091] L represents a divalent linking group. If there are multiple Ls, they may be the same or different. Examples of divalent linking groups include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, -COO-, -CONH-, -CO-, -O-, -SO2-, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO-alkylene group- are preferred, and -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene group-, or -OCO-alkylene group- are more preferred.

[0092] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0093] The aryl group may be monocyclic or polycyclic. Examples of aryl groups include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. Polycyclic groups are better able to suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocyclic groups include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. Examples of lactone and sultone rings include the lactone and sultone structures exemplified in the aforementioned resins. Among the heterocyclic groups, furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred.

[0094] The above-mentioned cyclic organic group may have substituents. Examples of such substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0095] An anion represented by general formula (3) is SO3 - -CF2-CH2-OCO-(L)q'-W, SO3 - -CF2-CHF-CH2-OCO-(L)q'-W, SO3 - -CF2-COO-(L)q'-W, SO3 - -CF2-CF2-CH2-CH2-(L)qW, or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W is preferred. Here, L, q, and W are the same as in general formula (3). q' represents an integer from 0 to 10.

[0096] Z in general formula (ZI) - and Z in general formula (ZII) - This may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0097] Examples of photoacid generators X include those disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, and paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345. These contents are incorporated herein by reference.

[0098] The photoacid generator X 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 form incorporated as part of a polymer may be used in combination. The photoacid generator X is preferably in the form of a low molecular weight compound. When the photoacid generator X is in the form of a low molecular weight compound, its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. If the photoacid generator X is incorporated into a polymer, it may be incorporated into a part of the aforementioned resin (P), or it may be incorporated into a resin different from resin (P). The photoacid generator X may be used alone or in combination of two or more types.

[0099] In the composition, the content of photoacid generator X (total if multiple types exist) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, even more preferably 1 to 20% by mass, and particularly preferably 1 to 15% by mass, based on the total solid content of the composition.

[0100] • Photoacid generator Y Photoacid generator Y is a photoacid generator with an onium salt structure that is relatively weak acidic relative to photoacid generator X. When a photoacid generator X and an onium salt that generates an acid that is relatively weaker than the acid produced by the photoacid generator X are mixed and used, when the acid produced by the photoacid generator X 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 appears to be deactivated, making it possible to control acid diffusion.

[0101] As the photoacid generator Y, compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

[0102] [ka]

[0103] In the formula, R 51 Z is a hydrocarbon group which may have substituents, 2c R is a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (provided that the carbon adjacent to S is not substituted with a fluorine atom), and 52 Y is an organic group, 3 Rf is a linear, branched, or cyclic alkylene group or arylene group, and Rf is a hydrocarbon group containing a fluorine atom, M + Each of these is independently an ammonium cation, a sulfonium cation, or an iodonium cation.

[0104] M + Preferred examples of sulfonium cations or iodonium cations represented as include the sulfonium cation exemplified by general formula (ZI) and the iodonium cation exemplified by general formula (ZII).

[0105] The onium salt (DC), which is a relatively weak acid with respect to the photoacid generator, may be a compound (hereinafter also referred to as "compound (DCA)") that has both a cationic and anionic moiety within the same molecule and in which the cationic and anionic moieties are covalently linked. As the compound (DCA), a compound represented by any of the following general formulas (C-1) to (C-3) is preferred.

[0106] [ka]

[0107] In general formulas (C-1) to (C-3), R1, R2, and R3 each independently represent a substituent having one or more carbon atoms. L1 represents a divalent linking group or single bond that connects the cation and anion moieties. -X - -COO - , -SO3 - , -SO2 - , and -N --R4 represents an anionic site selected from R4. R4 represents a monovalent substituent having at least one of the following at the linking site with the adjacent N atom: a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O)2-), and a sulfinyl group (-S(=O)-). R1, R2, R3, R4, and L1 may bond to each other to form a ring structure. In addition, in general formula (C-3), two of R1 to R3 may together represent a single divalent substituent, which may be bonded to the N atom by a double bond.

[0108] Examples of substituents having one or more carbon atoms in R1 to R3 include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyl groups, and arylaminocarbonyl groups. Preferably, alkyl groups, cycloalkyl groups, or aryl groups are used.

[0109] Examples of L1 as a divalent linking group include linear or branched alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these. Preferably, L1 is an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0110] The content of photoacid generator Y in the composition (total if multiple types exist) is 1.0 × 10⁻⁶, based on the total solid content of the composition. -4 Preferably, it is 1.0 × 10% or less by mass. -5 It is preferable that it be less than or equal to mass%.

[0111] Basic compounds Basic compounds function as acid diffusion control agents. Specifically, they trap acids generated from photoacid generators during exposure and act as quenchers to suppress the reaction of acid-degradable resins in unexposed areas caused by excess generated acid. Examples of acid diffusion control agents include basic compounds (CA), basic compounds (CB) whose basicity decreases or disappears upon irradiation with active light or radiation, low molecular weight compounds (CD) having a nitrogen atom and a group that is eliminated by the action of acid, and onium salt compounds (CE) having a nitrogen atom in the cation portion.

[0112] As the basic compound, any known acid diffusion control agent can be used as appropriate. For example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents. Furthermore, for example, specific examples of basic compounds (CA) are those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (CB) whose basicity is reduced or lost upon irradiation with active light or radiation are those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds (CD) having a nitrogen atom and a group that is eliminated by the action of an acid are those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824; and specific examples of onium salt compounds (CE) having a nitrogen atom in the cation are those described in paragraph

[0164] of International Publication No. 2020 / 066824. These contents are incorporated herein by reference.

[0113] As one embodiment of the basic compound, compound (CE) is preferred, and a compound having a basic moiety containing a nitrogen atom in the cation is more preferred. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. It is even more preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that electron-withdrawing functional groups (carbonyl groups, sulfonyl groups, cyano groups, halogen atoms, etc.) are not directly bonded to the nitrogen atom. A preferred example of compound (CE) is, but is not limited to, the compound disclosed in paragraph

[0203] of U.S. Patent Application Publication 2015 / 0309408A1.

[0114] Preferred examples of basic compounds are shown below, but the present invention is not limited to these.

[0115] [ka]

[0116] Basic compounds may be used individually or in combination of two or more. The content of basic compounds in the composition (the total amount if multiple types exist) is preferably 0.001 to 20% by mass, and more preferably 0.01 to 10% by mass, relative to the total solid content of the composition.

[0117] Solvents As the solvent, any known resist solvent can be used as appropriate. For example, known solvents disclosed in paragraphs

[0665] to

[0670] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0210] to

[0235] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0424] to

[0426] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0357] to

[0366] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used. Examples of solvents that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

[0118] As an organic solvent, a mixed solvent may be used, which is a mixture of a solvent having a hydroxyl group in its structure and a solvent that does not have a hydroxyl group. A solvent having a hydroxyl group and a solvent not having a hydroxyl group can be selected as appropriate, but as a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferred, and propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate (EL) is more preferred. Furthermore, preferred solvents that do not contain hydroxyl groups include alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compounds which may have a ring, cyclic lactone, or alkyl acetate. Among these, propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone are even more preferred. Propylene carbonate is also preferred as a solvent that does not contain hydroxyl groups. The mixing ratio (mass ratio) of the solvent having hydroxyl groups and the solvent not having hydroxyl groups is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and even more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50% by mass or more of the solvent not having hydroxyl groups is preferred in terms of uniform application. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be propylene glycol monomethyl ether acetate alone or a mixture of two or more solvents containing propylene glycol monomethyl ether acetate.

[0119] <<Other additives>> In addition to the components described above, the composition of the present invention may also appropriately contain surfactants, carboxylic acids, onium carboxylic acid salts, dissolution inhibitors with a molecular weight of 3000 or less as described in Proceedings of SPIE, 2724,355 (1996), dyes, plasticizers, photosensitizers, light absorbers, antioxidants, and the like.

[0120] Carboxylic acids can also be suitably used to improve performance. Aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferred as carboxylic acids. If the composition contains a carboxylic acid, the carboxylic acid content is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.01 to 3% by mass, relative to the total solid content of the composition.

[0121] As the surfactant, fluorine-based and / or silicone-based surfactants are preferred. These surfactants may be used individually or in combination of two or more types. If the composition contains a surfactant, the surfactant content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, and even more preferably 0.0005 to 1% by mass, relative to the total solid content of the composition.

[0122] The solid content concentration of the composition is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass.

[0123] (Preferred embodiment of negative-type photosensitive composition 2) Another example of a negative-type photosensitive composition that can be developed with alkali is a composition containing a polymerizable compound, a photopolymerization initiator, and a solvent. In the composition, the polymerizable compound is preferably an alkali-soluble component. Furthermore, it is preferable that the composition contains a resin. An alkali-soluble resin is preferred as the resin. The alkali-soluble resin can also be used as a dispersant or binder. When the composition contains an alkali-soluble resin, the resin content is preferably 0.1 to 40% by mass relative to the total solid content of the composition. Furthermore, if the polymerizable compound contains a cyclic ether group, a methylol group, or an alkoxymethyl group, it is preferable that the composition also contains a curing agent. Furthermore, the composition may contain components such as colorants (pigments, etc.), surfactants, polymerization inhibitors, silane coupling agents, ultraviolet absorbers, and antioxidants.

[0124] Examples of polymerizable compounds include compounds having polymerizable groups (polymerizable compounds). Examples of polymerizable groups include ethylenically unsaturated bond-containing groups, cyclic ether groups, methylol groups, and alkoxymethyl groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, vinylphenyl groups, (meth)allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, and (meth)acryloylamide groups. Examples of cyclic ether groups include epoxy groups and oxetanyl groups. The polymerizable compound may be a monomer or a polymer. When the polymerizable compound is a monomer, the number of polymerizable groups in the molecule is not particularly limited as long as there is one or more, two or more is preferred, and three or more is more preferred. There is no particular upper limit, but 15 or fewer is preferred, and 6 or fewer is more preferred. When the polymerizable compound is a polymer, a polymer containing repeating units having polymerizable groups is preferred.

[0125] When the polymerizable compound is a monomer, the molecular weight of the polymerizable compound is preferably less than 2,000, and more preferably 1,500 or less. The lower limit is preferably 100 or more, and more preferably 200 or more. When the polymerizable compound is a polymer, the weight-average molecular weight (Mw) of the polymerizable compound is preferably between 2,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

[0126] Polymerizable compounds may be used individually or in combination of two or more. The content of the polymerization compound is preferably 1 to 95% by mass relative to the total solid content of the composition.

[0127] Examples of solvents include water and organic solvents. Examples of organic solvents include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. The solvent may be used alone, or two or more solvents may be used in combination. The solvent content in the composition is preferably 10 to 97% by mass, relative to the total mass of the composition.

[0128] There are no particular restrictions on the photopolymerization initiator, and it can be appropriately selected from known photopolymerization initiators. For example, compounds that are photosensitive to light in the ultraviolet to visible regions are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0129] The photopolymerization initiator may be used alone or in combination of two or more types. The photopolymerization initiator content is preferably 0.1 to 40% by mass relative to the total solid content of the composition.

[0130] If the composition contains a compound having a cyclic ether group, the composition preferably further contains a curing agent. Examples of curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, polycarboxylic acids, and thiol compounds. When a curing agent is used, the curing agent content is preferably 0.01 to 20 parts by mass per 100 parts by mass of the compound having a cyclic ether group.

[0131] Examples of the above-mentioned alkaline-developable negative-type photosensitive compositions include curable compositions that can be used to form various cured films in the manufacturing process of solid-state image sensors (for example, curable compositions for making light-shielding films or color filters). Examples of such curable compositions include those disclosed in Japanese Patent Publication No. 2020-126253 and Japanese Patent Publication No. 2020-073989, etc.

[0132] Although the above mainly describes negative-type photosensitive compositions, the present invention can also be applied to the analysis of positive-type photosensitive compositions. The composition of the positive-type photosensitive composition is not particularly limited, and known compositions can be used. Examples include a photosensitive composition containing an acid-degradable resin having a group that decomposes upon the action of an acid to produce a polar group, and a photoacid generator. The above photosensitive composition may further contain other materials (e.g., acid diffusion control agents, hydrophobic resins, solvents, etc.).

[0133] <Method for producing a photosensitive composition> The method for producing the photosensitive composition of the present invention comprises the following composition preparation steps and analysis steps. Composition preparation step: A step in which a photosensitive composition is prepared. Analysis step: A step in which the photosensitive composition obtained in the composition preparation step is subjected to analysis based on the analytical method of the present invention. The method for preparing and analyzing the photosensitive composition is as previously described, and the preferred embodiment is also the same.

[0134] If the above analysis detects that the number of metal atoms derived from the photosensitive composition obtained through the composition preparation process is greater than the desired value, it is preferable to further purify the analyzed photosensitive composition. Furthermore, the analytical method of the present invention may be performed only once or multiple times after the preparation of the photosensitive composition.

[0135] A preferred embodiment of the manufacturing method of the present invention is a manufacturing method comprising the following steps: composition preparation, analysis, purification, and reanalysis. The above manufacturing method may further include a repeating step (one or more repeating steps) as needed. Composition preparation step: A step in which a photosensitive composition is prepared. Analysis step: A step in which the photosensitive composition obtained in the composition preparation step is subjected to analysis based on the analytical method of the present invention. Purification process: A process in which the photosensitive composition that has undergone the analysis process is further purified (for example, by filtration). Re-analysis step: A step in which the photosensitive composition that has undergone the purification step is subjected to analysis again according to the analytical method of the present invention. Repeated step: If the number of metal atoms derived from the photosensitive composition detected in the above reanalysis step does not meet a predetermined value, the above purification step and subsequent reanalysis step are repeated.

[0136] <Methods for manufacturing electronic devices> Furthermore, the present invention relates to a method for manufacturing an electronic device, which includes a step of performing an analysis based on the analysis 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]

[0137] The present invention will be described in more detail below based on 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 examples shown below. In the following, the coating film formed on the substrate after exposure treatment may be referred to as the "cured coating film" or "residual film," but these terms are all synonymous.

[0138] <Preparation of photosensitive compositions for examples and comparative examples> (Preparation of photosensitive compositions A-1 and A-1A: Negative type photosensitive compositions) Photosensitive compositions A-1 and A-1A were prepared as negative-type photosensitive compositions according to the following procedure. The abbreviations for the solvents are as follows. • EL: Ethyl lactate • PGME: Propylene glycol monomethyl ether • PGMEA: Propylene glycol monomethyl ether acetate

[0139] (Preparation of photosensitive composition A-1) Photosensitive composition A-1 was prepared by mixing the following components. • The following resin P-8: 57.7 parts by mass • The following photoacid generator A-12: 8.1 parts by mass • 5.0 parts by mass of the following photoacid generator B-1 • 1.0 parts by mass of the following basic compound Q-1 • Crosslinking agent X-1: 28.2 parts by mass • Solvent (a mixed solvent consisting of EL / PGME / PGMEA (mass ratio: 60 / 20 / 20)) ...the amount at which the solid content concentration reaches 2.6% by mass.

[0140] (Preparation of photosensitive composition A-1A) Photosensitive composition A-1A was prepared by mixing the following components. • The following resin P-8: 57.7 parts by mass • The following photoacid generator A-12: 8.1 parts by mass • 5.0 parts by mass of the following photoacid generator B-1 • 1.0 parts by mass of the following basic compound Q-1 • Crosslinking agent X-1: 28.2 parts by mass • Solvent (a mixed solvent consisting of EL / PGME / PGMEA (mass ratio: 60 / 20 / 20)) ...the amount at which the solid content concentration reaches 2.6% by mass. • Iron(III) stearate ...an amount equivalent to 10 ppb by mass of iron relative to the total mass of the photosensitive composition.

[0141] (Resin P-8)

[0142] [ka]

[0143] The numerical values ​​associated with each repeating unit in resin P-8 represent the molar ratio.

[0144] (Photoacid Generator A-12)

[0145] [ka]

[0146] (Photoacid Generator B-1)

[0147] [ka]

[0148] (Basic compound Q-1)

[0149] [ka]

[0150] (Crosslinking agent X-1) [ka]

[0151] (Filtration of photosensitive composition) Furthermore, the photosensitive compositions A-1 and A-1A prepared by the above procedure were subjected to the following purification treatment, and the purified compositions were used in each example. Specifically, photosensitive compositions A-1 and A-1A (both 12,000 g) were filtered using the following two-stage filters. Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0152] <Example 1: Formation of coating film (without exposure)> Photosensitive composition A-1A was connected to the resist line of a Tokyo Electron CleanTrack ACT8 coater. During the connection, no filter was connected to the connecting piping; instead, a dummy capsule was used. Next, the photosensitive composition connected using the method described above was applied to the aforementioned 8-inch (200 mm diameter) silicon wafer using a coater, and then baked at 90°C for 90 seconds to form a coating film (resist film). The thickness of the coating film at this time was adjusted to 80 nm. As mentioned above, no exposure treatment was performed in the above process. Furthermore, the substrate on which the coating film was formed was stored in a wafer case environment within a cleanroom until it was used for subsequent coating removal.

[0153] Next, the coating was removed from the coated silicon wafer obtained by performing the above procedure <Formation of coating (without exposure)> using an alkaline developer (removal solution). The removal solution used here is the alkaline developer X-W1 described later in (Preparation of the alkaline developer (removal solution used in step 2)).

[0154] (Preparation of alkaline developer (removal solution used in step 2)) As an alkaline developer, the following alkaline developer X was prepared. Alkaline developer X: Aqueous solution containing 2.38% by mass of tetramethylammonium hydroxide (TMAH). Next, alkaline developer X was subjected to POU (Point Of Use) filter filtration in the coater under the conditions shown below to obtain alkaline developer X-W1, which was used in the example. The "POU filter" refers to a filtration filter built into the apparatus for purification immediately before use, and an Entegris polyethylene filter with a pore size of 10 nm was used.

[0155] The coating was removed using a Tokyo Electron CleanTrack ACT8 connected to the removal solution before filtration. The POU filter mentioned above was connected to the connection piping during the connection process. Therefore, the alkaline developer X-W1 mentioned above refers to the alkaline developer obtained after passing through this POU filter. Thus, in the above coating removal procedure, the filtered removal solution, alkaline developer X-W1, is applied to the silicon wafer. The specific procedure for removing the above-mentioned coating was as follows: the coating solution was applied to the side of the coated silicon wafer where the coating was formed, using the method described above (dispensing at a flow rate of 600 mL / min for 30 seconds) with the coater connected to the coater's development line; and then baked at 100°C for 60 seconds to obtain a substrate with the coating removed.

[0156] For substrates from which the coating had been removed, the number of metal atoms on the substrate was measured using a total internal reflection X-ray fluorescence analyzer on the side of the silicon wafer where the coating had been formed. From the measurement results and the area value of the 8-inch (200 mm diameter) silicon wafer mentioned above, the number of metal atoms per unit area on the substrate was calculated. Hereafter, "the number of metal atoms per unit area on the substrate" will also be referred to as "the number of metal atoms."

[0157] <Comparative Example 1: Formation of a coating film (with exposure)> A coated silicon wafer was manufactured following the same procedure as in Example 1 described above. Next, using a KrF excimer laser immersion scanner (ASML; PAS5500 / 850C), the reading was taken in open frame at 50 mJ / cm². 2 The entire image was exposed with the specified exposure level. Subsequently, the substrate was heated at 130°C for 60 seconds (PEB), then subjected to alkaline development with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water, and then spin-dried. Due to the above-described full-surface exposure and alkaline development process, a residual film (cured coating film) was formed across the entire surface of the substrate. The number of metal atoms in the obtained substrate was measured using a total internal reflection X-ray fluorescence analyzer on the side of the silicon wafer where the residual film was formed, but no metal atoms could be detected.

[0158] The results for Example 1 and Comparative Example 1 are summarized below. Tables 1-9 shown below will be denoted as follows: In the table, in the "Type of Composition" column, "Negative" means that the composition is a negative-type photosensitive composition, and "Positive" means that the composition is a positive-type photosensitive composition. In the table, the "Intentional Addition of Metal Components" column indicates whether a metal compound containing metal atoms (in the case of photosensitive composition A-1A, this is iron(III) stearate) was intentionally used when preparing the photosensitive composition, and whether it was not used, by indicating "Yes". In the table, the "Post-coating exposure treatment" column indicates whether exposure treatment was performed on the coating film ("Yes") or not ("No"). In Table 1, the "Type of Removal Solution" column should be written as "Alkali" if an alkaline developer (Alkaline Developer X-W1) is used, and as "Solvent" if an organic solvent is used. The descriptions in the "Liquid Type" column of the table are as follows: • TMAH: Tetramethylammonium Hydroxide • ER6: A mixed solvent of PGMEA and PGME (mass ratio of PGMEA to PGME (PGMEA / PGME) = 6 / 4) CHN: Cyclohexanone nBA: Butyl acetate In the table, the "Presence or Absence of Residual Film" column indicates whether or not there is a residual film (cured coating film) on the substrate being analyzed using total internal reflection X-ray fluorescence analysis. "Present" indicates the presence of a residual film, and "Absent" indicates the absence of a residual film. In the table, the "Detection by Total Internal Reflectance X-ray Fluorescence Analysis" column indicates "Detectable" if the number of metal atoms can be measured, and "Not Detectable" if it cannot be measured.

[0159] [Table 1]

[0160] As shown in Table 1 above, metal atoms could be detected in Example 1, where the coating film was not exposed, but they could not be detected in Comparative Example 1, where the coating film was exposed. It is presumed that when a residual film is present on the substrate, as shown in Comparative Example 1, X-ray reflection does not occur, or the reflectance is significantly reduced, making it impossible to detect metal atoms.

[0161] <Example 2> The number of metal atoms was measured following the same procedure as in Example 1, except that photosensitive composition A-1 was used instead of photosensitive composition A-1A.

[0162] <Example 3> After removing the coating with a removal solution, the number of metal atoms was measured following the same procedure as in Example 2, except that a dry etching treatment using CF4 was performed on the silicon wafer surface from which the coating had been removed for the times shown in Table 2.

[0163] <Example 4> The number of metal atoms was measured following the same procedure as in Example 2, except that ER6 [a mixed solvent of PGMEA and PGME (mass ratio of PGMEA to PGME (PGMEA / PGME) = 6 / 4)] was used instead of the alkaline developer X-W1].

[0164] <Example 5> The number of metal atoms was measured according to the same procedure as in Example 3, except that ER6 was used instead of the alkaline developer X-W1.

[0165] <Example 6> The number of metal atoms was measured according to the same procedure as in Example 2, except that a dry etching treatment using CF4 was performed for the time shown in Table 2 to remove the coating film instead of the treatment of removing the coating film with the stripping solution (alkaline developer X-W1).

[0166] <Example 7> The number of metal atoms was measured according to the same procedure as in Example 6, except that the photosensitive composition B-1 described below was used instead of the photosensitive composition A-1.

[0167] (Photosensitive composition B-1) As a positive photosensitive composition, the photosensitive composition B-1 was prepared by the following procedure.

[0168] (Preparation of photosensitive composition B-1) The following components were mixed to prepare the photosensitive composition B-1. · 68.0 parts by mass of the following resin P-4 · 19.0 parts by mass of the following photoacid generator A-2 · 9.0 parts by mass of the following photoacid generator B-1 · 4.0 parts by mass of the following basic compound Q-4 · Solvent (a mixed solvent composed of EL / PGME / PGMEA (mass ratio: 40 / 20 / 40)) ··· An amount such that the solid content concentration becomes 2.6% by mass

[0169] (Resin P-4)

[0170] [Chemical formula]

[0171] The numerical values arranged along each repeating unit in the resin P-4 mean molar ratios. The Mw of the resin P-4 was 5900, and Mw / Mn was 1.5.

[0172] (Photoacid Generator A-2)

[0173] [ka]

[0174] (Photoacid Generator B-1)

[0175] [ka]

[0176] (Basic compound Q-4)

[0177] [ka]

[0178] (Filtration of photosensitive composition) Furthermore, the photosensitive composition B-1 (12000g) prepared by the above procedure was subjected to the following purification treatment, and the purified composition was used in the examples. Specifically, the photosensitive composition B-1 was filtered using the following two-stage filter. Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0179] <Example 8> The number of metal atoms was measured following the same procedure as in Example 2, except that photosensitive composition C-1, described later, was used instead of photosensitive composition A-1, and cyclohexanone (CHN) was used instead of the removal solution (alkaline developer X-W1).

[0180] (Photosensitive composition C-1) Cyclohexanone (102.3 parts by mass) was heated to 80 °C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by the following structural formula M-1 (22.2 parts by mass), a monomer represented by the following structural formula M-2 (22.8 parts by mass), a monomer represented by the following structural formula M-3 (6.6 parts by mass), cyclohexanone (189.9 parts by mass), and 2,2'-azobisisobutyric acid dimethyl [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (2.40 parts by mass) was dropped over 5 hours. After completion of the dropping, the mixture was further stirred at 80 °C for 2 hours. After allowing the reaction solution to cool, it was reprecipitated with a large amount of hexane / ethyl acetate (mass ratio 9:1), and the precipitate was filtered and collected. The obtained solid was dried under vacuum to obtain 41.1 parts by mass of an acid-decomposable resin (A-1).

[0181] [Chemical formula]

[0182] Regarding the obtained acid-decomposable resin (A-1), the weight average molecular weight (Mw: polystyrene conversion) determined by GPC (carrier: tetrahydrofuran (THF)) was Mw = 9500, and the dispersity was Mw / Mn = 1.60. 13 The composition ratio (molar ratio) measured by C-NMR was 40 / 50 / 10 in order from the left-side structure.

[0183] Next, a photosensitive composition C-1 was prepared by mixing the following components. · Acid-decomposable resin (resin A-1 described above): 1,267 g · Photoacid generator (PAG-7 shown below): 101 g · Quencher (C-1 shown below): 22 g · Hydrophobic resin (P'-5 shown below): 10 g · PGMEA: 38,600 g

[0184] [Chemical formula]

[0185] [Chemical formula]

[0186] [ka]

[0187] The numerical values ​​associated with each repeating unit in the hydrophobic resin (P'-5) represent the molar ratio.

[0188] Furthermore, the photosensitive composition C-1 prepared by the above procedure was subjected to the filtration treatment shown below, and the purified composition was used in the examples.

[0189] The photosensitive composition (12,000 g) was filtered using the following two-stage filter. Stage 1: PALL nylon filter with a pore size of 5nm. Second row: Entegris polyethylene filter with a pore size of 1 nm.

[0190] <Example 9> The number of metal atoms was measured following the same procedure as in Example 8, except that butyl acetate (nBA) was used instead of cyclohexanone (CHN).

[0191] In Tables 2-9, the "Gas Removal" column indicates "Yes" if dry etching or coating removal by dry etching was performed using the gas specified in the "Gas Type" column.

[0192] [Table 2]

[0193] As shown in Table 2, it was confirmed that the desired effect could be obtained even when the method of removing the coating film was changed. Furthermore, in the photosensitive composition A-1 used in Example 2, metal atoms were detected despite the fact that no metal components were intentionally added. This is presumed to be due to the detection of trace amounts of metal atoms contained in the raw materials used to prepare the photosensitive composition, or trace amounts of metal atoms that were mixed in during the preparation of the photosensitive composition.

[0194] <Examples 11-12> The number of metal atoms was measured following the same procedure as in Example 2, except that the processing time for removing the coating film using the removal solution was changed to the time shown in the "Processing time for processing using the removal solution" column in Table 3.

[0195] <Example 13> An aqueous solution containing 2% by mass of hydrogen peroxide and 2% by mass of hydrogen fluoride was dropped onto a substrate from which the coating had been removed. The aqueous solution was then scanned across the substrate to allow it to aggregate near the center, and then evaporated and dried. The number of metal atoms on this substrate was measured using total internal reflection X-ray fluorescence analysis in the same manner as described above, except that the number of metal atoms on the substrate was measured and the measurement value was obtained, following the same procedure as in Example 2.

[0196] <Examples 14-15> The number of metal atoms was measured following the same procedure as in Example 13, except that the processing time for the treatment to remove the coating film using the removal solution was changed to the time shown in the "Processing time for treatment using the removal solution" column in Table 3.

[0197] <Examples 16-17> The number of metal atoms was measured following the same procedure as in Example 3, except that the processing time for dry etching (gas removal treatment) using CF4 on the silicon wafer surface after the coating film removal treatment with the removal solution was changed to the time shown in the "Processing Time for Gas Removal Treatment" column of Table 3.

[0198] <Example 18> An aqueous solution containing 2% by mass of hydrogen peroxide and 2% by mass of hydrogen fluoride was dropped onto a substrate from which the coating had been removed. The aqueous solution was then scanned across the substrate to allow it to aggregate near the center, and then evaporated and dried. The number of metal atoms on this substrate was measured using total internal reflection X-ray fluorescence analysis in the same manner as described above, except that the number of metal atoms on the substrate was measured and the measured value was obtained by following the same procedure as in Example 3.

[0199] <Examples 19-20> The number of metal atoms was measured following the same procedure as in Example 18, except that the processing time for the gas removal treatment was changed to the time shown in the "Processing Time for Gas Removal Treatment" column in Table 3.

[0200] In Examples 11-20, each operation was performed five times to evaluate the variability of the measured number of metal atoms. We categorized the results as follows: "A" for cases with little variation, "B" for cases with some variation, "C" for cases with moderate variation, and "D" for cases with large variation.

[0201] In Table 3, the "Concentration and Accumulation" column indicates "Yes" when a concentration operation using an aqueous solution containing hydrogen fluoride and hydrogen peroxide is performed (an operation in which an aqueous solution containing hydrogen fluoride and hydrogen peroxide is dropped, scanned across the substrate to cause the aqueous solution to condense near the center of the substrate, and then evaporated and dried). In Table 3, the "Amount of Residual Metal on Wafer" column shows the relative number of metal atoms when total internal reflection X-ray fluorescence analysis is performed. Specifically, the number of metal atoms in Examples 11 and 12 is expressed as a relative amount based on the number of metal atoms in Example 2 (ref1), the number of metal atoms in Examples 14 and 15 is expressed as a relative amount based on the number of metal atoms in Example 13 (ref2), the number of metal atoms in Examples 16 and 17 is expressed as a relative amount based on the number of metal atoms in Example 3 (ref3), and the number of metal atoms in Examples 19 and 20 is expressed as a relative amount based on the number of metal atoms in Example 18 (ref4). "Medium" means a range of 0.3 to 0.7 times the reference value, and "Small" means less than 0.3 times the reference value. Note that "Medium (numerical value)" and "Small (numerical value)" mean that the numerical value in parentheses is used as the reference data. For example, "Medium (1)" means data based on ref1. In Table 3, the "direct-TXRF" column shows the results of total internal reflection X-ray fluorescence analysis performed without the "concentration and accumulation" process described above, while the "concentrated-TXRF" column shows the results of total internal reflection X-ray fluorescence analysis performed with the "concentration and accumulation" process described above.

[0202] [Table 3]

[0203] As shown in Table 3, as the coating removal time (processing time using the removal solution, processing time for gas removal) increased, the amount of remaining metal on the wafer decreased, and the variability of the measured values ​​tended to increase. Furthermore, by performing the concentration process (step 5), even though the amount of residual metal decreased, the variability in the measured values ​​was suppressed.

[0204] Photosensitive compositions D to N were prepared by mixing each component based on the compositions shown in Table 4, which will be described later.

[0205] [Table 4]

[0206] In Table 4, the "Solvent" column represents the content (mass%) of each solvent in 100% by mass of the solvent. In Table 4, the "Solid Content Concentration" column represents the concentration (mass%) of solid content in the photosensitive composition. In Table 4, resin P-8, photoacid generator A-12, photoacid generator B-1, basic compound Q-1, crosslinking agent X-1, PGME, and PGMEA are as described above. Other compounds in Table 4 are as follows:

[0207] [ka]

[0208] [ka]

[0209] The content of each repeating unit relative to the total repeating units in the above resin F-1 was 85 mol%, 10 mol%, and 5 mol%, from left to right. The content of each repeating unit relative to the total repeating units in the resin F-2 described above was 30 mol%, 60 mol%, and 10 mol%, from left to right. The content of each repeating unit relative to the total repeating units in the above resin F-3 was 40 mol%, 50 mol%, 5 mol%, and 5 mol%, respectively, from left to right.

[0210] <Examples 21-31> The number of metal atoms was measured following the same procedure as in Example 2, except that photosensitive compositions D to N were used instead of photosensitive composition A-1, as shown in Table 5.

[0211] <Examples 32-42> The number of metal atoms was measured following the same procedure as in Example 13, except that photosensitive compositions D to N were used instead of photosensitive composition A-1, as shown in Table 6.

[0212] <Examples 43-53> The number of metal atoms was measured following the same procedure as in Example 3, except that photosensitive compositions D to N were used instead of photosensitive composition A-1, as shown in Table 7.

[0213] <Examples 54-64> The number of metal atoms was measured following the same procedure as in Example 18, except that photosensitive compositions D to N were used instead of photosensitive composition A-1, as shown in Table 8.

[0214] [Table 5]

[0215] [Table 6]

[0216] [Table 7]

[0217] [Table 8]

[0218] In Tables 5-8, the "Amount of Residual Metal on Wafer" column shows the relative number of metal atoms when total internal reflection X-ray fluorescence analysis is performed. Specifically, the number of metal atoms in Examples 21-31 is expressed as a relative amount based on the number of metal atoms in Example 2 (ref1), the number of metal atoms in Examples 32-42 is expressed as a relative amount based on the number of metal atoms in Example 13 (ref2), the number of metal atoms in Examples 43-53 is expressed as a relative amount based on the number of metal atoms in Example 3 (ref3), and the number of metal atoms in Examples 54-64 is expressed as a relative amount based on the number of metal atoms in Example 18 (ref4). "Same" means a range of 0.9 to 1.1 times the reference value. Note that "Same (numerical value)" means that the numerical value in parentheses is used as the reference data. For example, "Same (1)" means data based on ref1.

[0219] As shown in Tables 5-8, the desired effect was obtained even when the type of photosensitive composition was changed.

[0220] Next, the number of defects was evaluated using the photosensitive compositions A-1 to N described above. Specifically, we first used a KLA-Tencor SP5 dark-field defect inspection system to perform defect inspection on a 12-inch (300 mm diameter) silicon wafer used for the inspection, and measured the number of defects (defect count) with a size of 20 nm or larger present on the surface of the silicon wafer ("EX: Original substrate defect count").

[0221] Furthermore, in the measurement of the number of defects on the surface of a 12-inch (300 mm diameter) silicon wafer using the SP5 dark-field defect inspection system manufactured by KLA Tencor, as described below, the concentric circles of the 12-inch (300 mm diameter) silicon wafer with an area of ​​660 cm² are used. 2 The area within the circle (in other words, a circle centered on the center of the above 12-inch (300 mm diameter) silicon wafer, with an area of ​​660 cm²) 2 The area within the circle is used as the inspection area. Furthermore, Table 9, described later, shows the results of measuring the number of defects on the surface of a 12-inch (300 mm diameter) silicon wafer using the SP5 dark-field defect inspection system manufactured by KLA Tencor, including the number of defects in the area within the circle (unit: defects) and the number of defects per unit area (unit: defects / cm²). 2 This indicates that...

[0222] Next, the removal solutions used in each example shown in Table 9 were connected to the developing line of the CleanTrack ACT12 coater manufactured by Tokyo Electron Corporation. The POU filters mentioned above were connected to the connecting pipes during the connection process. Next, the removal solution connected using the method described above was applied to the 12-inch (300 mm diameter) silicon wafer, which had been pre-checked for defects as described above, using a coater (dispensing at a flow rate of 600 mL / min for 30 seconds), and then baked at 100°C for 60 seconds. The number of defects larger than 20 nm on the surface of the silicon wafer, obtained by the above procedure after coating with the removal solution, was measured using a dark-field defect inspection system SP5 manufactured by KLA Tencor ("F: Number of defects after coating with removal solution"). Next, based on the results of "EX: Number of defects in the original substrate" and "F: Number of defects after application of the removal solution" obtained from the above various inspections, "C: Number of defects in the removal solution" was calculated using the following formula. Formula (A1): [C: Number of defects in the removal solution] = [F: Number of defects after application of the removal solution] - [EX: Number of defects in the original substrate]

[0223] Based on the above tests, the initial number of defects in the removal solution ([C: Number of defects in removal solution]) listed in Table 9 is 100 or less (0.15 defects / cm²). 2 It was confirmed that the following applies:

[0224] Next, 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 SP5 manufactured by KLA Tencor, and the number of defects larger than 20 nm on the surface of the silicon wafer was measured ("E: Number of defects in the original substrate").

[0225] Each photosensitive composition used in the example was connected to the resist line of a Tokyo Electron CleanTrack ACT12 coater (note that no filters were connected to the connection piping; instead, dummy capsules were used). Next, the photosensitive composition connected using the method described above was applied to the 12-inch (300 mm diameter) silicon wafer used for inspection, and then baked at 90°C for 90 seconds to form a coating. The thickness of the resist film (coating) at this time was adjusted to 80 nm. As mentioned above, no exposure treatment was performed in the above process. Furthermore, the substrate on which the resist film was formed was stored in a wafer case environment within a cleanroom until it was subjected to the resist film removal process described later.

[0226] Next, the resist film was removed from the silicon wafer with the resist film obtained by performing the above procedure using the removal solutions listed in Table 9. For example, in Example X1, the resist film formed using photosensitive composition A-1 was removed using an alkaline developer (alkaline developer X-W1). In Example 2, ER6 was used as the removal solution, and in Example 3, CHN was used as the removal solution. The removal was performed using a Tokyo Electron CleanTrack ACT12 connected to the removal solution. During connection, the aforementioned POU filter was connected to the connecting piping. The specific procedure for the above removal involved applying the removal solution, connected to the coater's development line, to the silicon wafer with the resist film using the method described above (dispensing at a flow rate of 600 mL / min for 30 seconds), and then baking it at 100°C for 60 seconds.

[0227] Following the above process, the wafer from which the resist film had been removed was subjected to defect inspection using a dark-field defect inspection system SP5 manufactured by KLA Tencor, and the number of defects with a size of 20 nm or larger on the surface of the silicon wafer was measured ([D: Total number of defects after solvent removal treatment]).

[0228] Next, based on the results of "E: Number of defects in the original substrate," "D: Total number of defects after solvent removal treatment," and "C: Number of defects in the removal solution" obtained from the various inspections described above, "A: Number of defects in the resist" was calculated using the following formula. Formula: [A: Number of resist defects] = [D: Total number of defects after solvent removal treatment] - [E: Number of defects in the original substrate] - [C: Number of defects in the removal solution] The "Number of defects [pieces]" column in Table 9 shows the value of the number of resist defects indicated in [A: Number of resist defects] above, and is labeled as "Number of defects [pieces / cm²]". 2 The column "[ ]" indicates the value of the number of resist defects per unit area.

[0229] [Table 9]

Claims

1. Step 1 involves applying a photosensitive composition onto a substrate to form a coating film, Step 2 involves removing the coating film from the substrate without exposure to light to obtain a substrate with the coating film removed. A method for analyzing a photosensitive composition, comprising step 3: measuring the number of metal atoms per unit area on the substrate from which the coating film has been removed using total internal reflection X-ray fluorescence analysis, and obtaining a measured value.

2. The method for analyzing a photosensitive composition according to claim 1, further comprising step 4 between step 2 and step 3, in which a gas containing hydrogen fluoride gas is brought into contact with the substrate from which the coating film has been removed.

3. The method for analyzing a photosensitive composition according to claim 1 or 2, further comprising step 5 between step 2 and step 3, in which the substrate from which the coating film has been removed is scanned with a solution containing hydrogen fluoride and hydrogen peroxide, and metal atoms on the substrate from which the coating film has been removed are recovered into the solution.

4. The method for analyzing a photosensitive composition according to claim 1 or 2, wherein in step 2, the coating film is removed using a solution.

5. The method for analyzing a photosensitive composition according to claim 4, wherein the solution is selected from the group consisting of an aqueous solution containing tetramethylammonium hydroxide, an ester-based organic solvent, an alcohol-based organic solvent, and a ketone-based organic solvent.

6. The method for analyzing a photosensitive composition according to claim 4, wherein the solution is 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.

7. The method for analyzing a photosensitive composition according to claim 4, wherein in step 2, the time for removing the coating film is 300 seconds or less.

8. The method for analyzing a photosensitive composition according to claim 7, wherein the time for removing the coating film is 180 seconds or less.

9. The method for analyzing a photosensitive composition according to claim 1 or 2, wherein in step 2, the coating film is removed using a gas.

10. The method for analyzing a photosensitive composition according to claim 9, wherein the gas is selected from the group consisting of fluorine-based gases, oxygen-based gases, and noble gases.

11. The method for analyzing a photosensitive composition according to claim 9, wherein in step 2, the time for removing the coating film is 300 seconds or less.

12. The method for analyzing a photosensitive composition according to claim 11, wherein the time for removing the coating film is 180 seconds or less.

13. A step of preparing a photosensitive composition, A method for producing a photosensitive composition, comprising the step of performing the analytical method described in claim 1 or 2 on the prepared photosensitive composition.

14. A method for manufacturing an electronic device, comprising the step of carrying out the analysis method described in claim 1 or 2.

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