Substrate manufacturing method

Abstract

One aspect of the present invention may provide a substrate manufacturing method including an analysis step whereby the concentration of an additive in a chemical solution in addition to the concentration of an alkali agent in the chemical solution can be analyzed.One aspect disclosed herein relates to a substrate manufacturing method including the following steps 1 and 2.　One aspect disclosed herein relates to a substrate manufacturing method including the following steps 1 and 2. Step 1: A step for treating a substrate to be treated with a chemical solution containing an alkali agent and an additive. Step 2: A step for performing acid titration of the chemical solution used in step 1 and measurement of the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution by using the obtained titration value and Brix value, wherein the additive contains a surfactant and / or a solvent.

Description

Method for manufacturing substrate

[0001] The present disclosure relates to a method for manufacturing a substrate, a method and an apparatus for analyzing concentrations of an alkali agent and an additive in a chemical solution, and a method for manufacturing an electronic component.

[0002] In recent years, low power consumption, higher processing speed, and size reduction have advanced in personal computers and various electronic devices, and wirings such as package substrates mounted thereon have been increasingly miniaturized year by year. The metal mask method has been mainly used conventionally for forming such fine wirings and connection terminals such as pillars and bumps, but it is being replaced by other new methods due to its low versatility and difficulty in coping with the miniaturization of wirings and the like.

[0003] As one of the new methods, a method of using a dry film resist as a thick resin mask instead of a metal mask is known. This resin mask is finally peeled and removed, and an alkaline chemical solution (for example, a stripper composition, a cleaning agent for peeling a resin mask) is used in this step.

[0004] It has been reported that alkaline chemical solutions deteriorate due to dissolution of resist, reaction with carbon dioxide in air, and the like, resulting in decreased stripping performance (resin mask removability). Therefore, various methods for suppressing deterioration of the chemical solution and extending its service life have been studied. For example, Japanese Unexamined Patent Application Publication No. 2003-122029 (Patent Document 1) discloses that carbon dioxide absorbed in a resist stripping solution is the main factor that reduces resist stripping performance, and proposes a method for managing a resist stripping solution that maintains the carbon dioxide concentration in the resist stripping solution at 3% by weight or less.

[0005] In one aspect, the present disclosure relates to a method for manufacturing a substrate including the following Step 1 and Step 2. Step 1: a step of treating a substrate to be treated with a chemical solution containing an alkali agent and an additive. Step 2: a step of performing acid titration of the chemical solution used in Step 1 and measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value, provided that the additive contains a surfactant and / or a solvent.

[0006] This disclosure relates, in one embodiment, to a concentration analysis method for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution comprises an alkaline agent and an additive, the additive comprising a surfactant and / or a solvent, and the concentration analysis method comprising the steps of: acid titrating the chemical solution; measuring the Brix value of the chemical solution; and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value.

[0007] This disclosure relates, in one embodiment, to a concentration analyzer for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution comprises an alkaline agent and an additive, the additive comprises a surfactant and / or a solvent, and includes a titration unit for acid titrating the chemical solution, a Brix measurement unit for measuring the Brix value of the chemical solution, and a calculation unit for calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value.

[0008] This disclosure relates, in one embodiment, to a method for manufacturing an electronic component, which includes a step of analyzing the concentrations of an alkaline agent and an additive in a chemical solution used in a step of peeling off a resin mask, using the concentration analysis method of this disclosure.

[0009] Figure 1 is a schematic diagram showing one embodiment of a substrate processing system having the concentration analyzer of the present disclosure. Figure 2 is a schematic diagram showing one embodiment of a substrate processing system having the concentration analyzer of the present disclosure.

[0010] When alkaline chemical solutions (e.g., stripping agent compositions) are reused in cycles, the alkaline components and carbon dioxide concentrations in the solution change, requiring the replenishment, mixing, or replacement of the solution or its components according to the results of concentration analysis. The amount to be replenished and the mixing ratio must be managed to appropriately maintain the composition of the solution and prevent a decrease in the resin mask stripping ability (resin mask removal ability, cleaning ability). The standard method for analyzing the concentration of alkaline agents in alkaline chemical solutions containing alkaline agents as active ingredients is titration analysis (alone). However, if the alkaline chemical solution does not contain strong alkalis such as quaternary ammonium hydroxide, for example, if it contains additives such as surfactants or solvents as active ingredients, titration analysis alone may not be able to measure (analyze) the concentration of such additives in the solution.

[0011] Therefore, this disclosure provides, in one or more embodiments, a method for manufacturing a substrate that includes an analytical step capable of analyzing the concentration of an additive in a chemical solution in addition to the concentration of an alkaline agent in the chemical solution, a concentration analysis method and concentration analysis apparatus capable of analyzing the concentration of an additive in a chemical solution in addition to the concentration of an alkaline agent in the chemical solution, and a method for manufacturing an electronic component using the concentration analysis method.

[0012] According to this disclosure, in one embodiment, a method for manufacturing a substrate can be provided that includes an analytical step capable of analyzing not only the concentration of an alkaline agent in the chemical solution but also the concentration of additives in the chemical solution.

[0013] In addition to TMAH-based stripping solutions using tetramethylammonium hydroxide (TMAH), non-TMAH-based stripping solutions using NaOH have also been proposed for stripping resin masks. Non-TMAH-based stripping solutions using NaOH may contain additives such as surfactants and solvents. However, the concentration of such additives is difficult to analyze by conventional titration methods. Therefore, the inventors have found a method to analyze the concentration of additives in the stripping solution by using titration and Brix measurement. Here, one example of a titration method is potentiometric titration. Potentiometric titration is a method of detecting the inflection point of the potentiometric curve (titration curve) during titration. For measurement by potentiometric titration, a known measuring device (for example, an automatic potentiometric titrator) can be used. An example of an acid used for titration is hydrochloric acid. The titration temperature is not particularly limited and is usually room temperature. Furthermore, an inflection point is the point where the tangent line to the titration curve intersects the titration curve at a point of tangency. Inflection points can be determined, for example, by detecting the point where the second derivative of the titration curve changes sign from negative to positive, or by detecting the minimum value of the first derivative of the titration curve. In this disclosure, Brix measurement refers to a measurement method using a Brix meter, which can measure the concentration of a solution by utilizing the refraction of light. The value obtained by Brix measurement is called the Brix value, and the Brix value corresponds to the mass percentage of a sucrose solution at 20°C.

[0014] This disclosure relates in one embodiment to a method for manufacturing a substrate (hereinafter also referred to as "the substrate manufacturing method of this disclosure"), comprising the following steps 1 and 2. Step 1: A step of treating a substrate to be treated with a chemical solution containing an alkaline agent and an additive. Step 2: A step of performing an acid titration of the chemical solution used in step 1 and measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. However, the additive includes a surfactant and / or a solvent.

[0015] According to this disclosure, in one or more embodiments, a method for manufacturing a substrate is provided that includes an analytical step capable of analyzing not only the concentration of the alkaline agent in the chemical solution but also the concentration of the additive in the chemical solution. As a result, in one or more embodiments, since both the concentration of the alkaline agent and the additive in the chemical solution can be determined, the amount of components in the chemical solution used in step 1 can be adjusted based on both the alkaline agent and the additive.

[0016] While the detailed mechanism of action of the effects of this disclosure is unclear, it is presumed to be as follows: Unlike alkaline agents, additives such as surfactants and solvents cannot be analyzed by acid titration. On the other hand, aqueous solutions of these additives can be analyzed by Brix measurement because the refractive index of light changes. However, in chemical solutions containing both additives and alkaline agents, the refractive index of light changes due to the alkaline agent, making it difficult to accurately analyze the additives by Brix measurement. In this disclosure, it is considered that even in chemical solutions containing both additives and alkaline agents, the alkaline agent can be analyzed by acid titration, and the degree of change in the refractive index of light due to the alkaline agent can be calculated from a calibration curve and corrected from the Brix value of the chemical solution, thereby enabling accurate analysis of the additive concentration. Therefore, according to this disclosure, the additive concentration can be calculated after correcting for the contribution from the alkaline agent included in the Brix value, making it possible to manage chemical solutions considering the additive concentration. However, this disclosure does not have to be interpreted as being limited to this mechanism.

[0017] [Step 1: Processing] Step 1 in the substrate manufacturing method of the present disclosure is a step of processing a substrate to be processed with a chemical solution containing an alkaline agent and an additive, in one or more embodiments.

[0018] In one or more embodiments, the process in step 1 is cleaning the substrate to be processed. In one or more embodiments, the process in step 1 is processing a substrate (substrate to be processed) having a resin mask using the chemical solution. In one or more embodiments, the process includes peeling the resin mask off the substrate having the resin mask. Peeling off the resin mask includes cleaning the substrate having the resin mask and removing the resin mask from the substrate having the resin mask. Therefore, in one or more embodiments, step 1 is a step of peeling the resin mask off a substrate (substrate to be processed) having a resin mask using the chemical solution. In one or more other embodiments, the process in step 1 is processing a substrate (substrate to be processed) having flux residue. In one or more other embodiments, the process includes cleaning the substrate having flux residue and removing the flux residue from the substrate having flux residue. In one or more other embodiments, the process in step 1 is processing a wafer (substrate to be processed) to which wafer processing adhesive (temporary fixing adhesive) is attached. In one or more other embodiments, the process includes cleaning a wafer to which wafer processing adhesive has adhered, and removing the adhesive from the wafer to which wafer processing adhesive has adhered. Step 1 includes bringing a chemical solution into contact with a substrate to be processed in one or more embodiments.

[0019] In this disclosure, methods for treating a substrate with a chemical solution, methods for peeling a resin mask from a substrate using a chemical solution, methods for cleaning a substrate with a chemical solution, or methods for bringing a chemical solution into contact with a substrate include, for example, immersing the substrate in a cleaning bath containing the chemical solution, spraying the chemical solution onto the substrate (shower method), ultrasonic cleaning methods in which ultrasonic waves are irradiated onto the substrate while it is immersed in the chemical solution, methods of pouring the chemical solution over the substrate, and paddle cleaning methods of the substrate with the chemical solution. In one or more embodiments, the chemical solution in this disclosure can be used directly for treatment (cleaning) without dilution. Examples of substrates to be treated include those described later. For example, step 1, in one or more embodiments, includes spraying the chemical solution onto a substrate having a resin mask (substrate to be treated). Examples of the time for contacting or immersing the substrate with the chemical solution (contact time or immersion time) include, for example, 1 minute or more and 10 minutes or less, and more specifically, 2 minutes or more and 6 minutes or less. When the liquid chemical is sprayed and applied to the surface, the spraying time can be, for example, between 1 minute and 10 minutes, or between 2 minutes and 6 minutes.

[0020] In step 1, it is preferable to irradiate the substrate to be treated with ultrasound when the chemical solution comes into contact with it, in order to easily demonstrate the processing capacity of the chemical solution (peeling and cleaning power, resin mask peeling ability, resin mask removal ability, and cleaning ability), and it is more preferable that the ultrasound is of a relatively high frequency. From the same viewpoint, the irradiation conditions for the ultrasound are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.

[0021] In step 1, the processing capacity of the chemical solution (peeling and cleaning power, resin mask peeling ability, resin mask removal ability, and cleaning ability) is easily demonstrated, so the temperature at which the chemical solution is used (processing temperature) is preferably 40°C or higher, more preferably 50°C or higher, and from the viewpoint of reducing the impact on the substrate, it is preferably 70°C or lower, and more preferably 60°C or lower.

[0022] In one or more embodiments, step 1 may further include rinsing the substrate to be treated with water after bringing it into contact with the chemical solution, and then drying it. Examples of rinsing methods include running water rinsing. Examples of drying methods include air blow drying. In one or more embodiments, step 1 may further include rinsing the substrate to be treated with water after bringing it into contact with the chemical solution.

[0023] In this disclosure, a resin mask is a mask that protects the surface of a material from processes such as etching, plating, and heating, i.e., a mask that functions as a protective film. Examples of resin masks include a resist layer after exposure and development, a resist layer that has undergone at least one of exposure and / or development (hereinafter also referred to as "exposed and / or developed"), or a cured resist layer. In addition, in one or more embodiments, the resin mask is formed using a resist whose physical properties, such as solubility in a developer solution, change when exposed to light or electron beams. Resists are broadly classified into negative and positive types based on their reaction method with light or electron beams. Negative resists have the characteristic of decreasing solubility in a developer solution when exposed, and a layer containing a negative resist (hereinafter also referred to as the "negative resist layer") is used as a resin mask in the exposed area after exposure and development. Positive resists have the property of increasing solubility in developer when exposed to light. After exposure and development, the exposed areas of a layer containing a positive resist (hereinafter also referred to as the "positive resist layer") are removed, and the unexposed areas are used as a resin mask. By using a resin mask with such properties, fine connection parts of a circuit board, such as metal wiring, metal pillars, and solder bumps, can be formed. In one or more embodiments, the resin material used to form the resin mask is a film-like photosensitive resin, a resist film, or a photoresist. General-purpose resist films can be used.

[0024] <Chemical Solution Used in Step 1> In one or more embodiments, the chemical solution used in Step 1 is a release agent composition for peeling off a resin mask. In one or more other embodiments, the chemical solution used in Step 1 is a flax residue removal cleaning agent composition for removing flux residue from a substrate having flux residue. In one or more other embodiments, the chemical solution used in Step 1 is a cleaning agent composition for removing wafer processing adhesive from a wafer on which the adhesive has adhered to the surface. In one or more embodiments, the chemical solution used in Step 1 is a chemical solution comprising an alkaline agent and an additive. In one or more embodiments, the chemical solution used in Step 1 can be prepared by compounding an alkaline agent, an additive, and water as needed. In this disclosure, "compounding" includes mixing the alkaline agent, the additive, and water as needed simultaneously or in any order.

[0025] (Alkaline agent) In one or more embodiments, the alkaline agent contained in the chemical solution used in step 1 contains an inorganic alkali, and in one or more embodiments, it is an inorganic alkali. In one or more embodiments, the alkaline agent in step 1 contains an alkali hydroxide. In one or more embodiments, the inorganic alkali is at least one selected from alkali metal hydroxides and carbonates, and in one or more embodiments, it is an alkali metal hydroxide and an alkali metal carbonate. Examples of alkali metal hydroxides include sodium hydroxide (NaOH) and potassium hydroxide (KOH). Examples of alkali metal carbonates include sodium carbonate (Na2CO3) and potassium carbonate (K2CO3). In one or more embodiments, the inorganic alkali is preferably at least one selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), and potassium carbonate (K2CO3). In one or more embodiments, the alkaline agent contained in the chemical solution used in step 1 is NaOH, and in one or more other embodiments, it is NaOH and Na2CO3. The aforementioned alkaline agent may be one type or a combination of two or more types.

[0026] The content (concentration) of the alkaline agent in the chemical solution used in step 1 is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of improving the peelability of the resin mask, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of improving the peelability of the resin mask and wastewater treatment. More specifically, the content (concentration) of the alkaline agent in the chemical solution used in step 1 is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 12% by mass or less, and even more preferably 2% by mass or more and 10% by mass or less. If there is a combination of two or more alkaline agents, the content of the alkaline agent is the total content of those agents.

[0027] (Additives) In one or more embodiments, the additives contained in the chemical solution used in step 1 preferably do not contain or substantially contain quaternary ammonium hydroxide. For example, the content of quaternary ammonium hydroxide in the additive is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the additive contains a surfactant and / or a solvent. In one or more embodiments, the surfactant and / or solvent is an active ingredient for improving the peelability of the resin mask (resin mask removal, cleaning ability). In one or more embodiments, the additive is a mixture or aqueous solution of a plurality of components including the surfactant and solvent described below. From the viewpoint of improving the peelability of the resin mask, the content of the additive in the chemical solution used in step 1 is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and from the viewpoint of improving the peelability of the resin mask, it is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. More specifically, the content of the additive in the chemical solution used in step 1 is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less. If there is a combination of two or more additives, the content of the additive is the total content of those additives.

[0028] <Surfactants> In one or more embodiments, the additive includes a surfactant. The surfactant may be one type or a combination of two or more types. From the viewpoint of improving resin mask peelability, the surfactant is preferably a nonionic surfactant in one or more embodiments. Examples of nonionic surfactants include polyoxyethylene alkyl ethers. From the viewpoint of improving resin mask peelability, the alkyl group of the polyoxyethylene alkyl ether is preferably a hydrocarbon group having 8 to 22 carbon atoms, and more preferably a linear or branched alkyl group having 10 to 20 carbon atoms. Examples of the alkyl group include at least one selected from octyl group, 2-ethylhexyl group, decyl group, isodecyl group, 2-propylheptyl group, dodecyl group, tridecyl group, tetradecyl group, and 2-octyldodecyl group. The average number of moles of ethyleneoxy groups added to the polyoxyethylene alkyl ether is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, from the viewpoint of improving resin mask peelability, and preferably 12 or less, more preferably 10 or less, even more preferably 9 or less, more specifically preferably 3 to 12, more preferably 4 to 10, and even more preferably 5 to 9. Examples of surfactants include polyoxyethylene (9) lauryl ether. The numbers in parentheses indicate the average number of moles added. The surfactant content in the additive is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, from the viewpoint of improving resin mask peelability, and preferably 50% by mass or less, more preferably 35% by mass or less, and even more preferably 20% by mass or less. More specifically, the surfactant content in the additive is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 35% by mass or less, even more preferably 5% by mass or more and 20% by mass or less. When there is a combination of two or more surfactants, the surfactant content is the total content of those surfactants.The surfactant content in the chemical solution used in step 1 is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of improving the peelability of the resin mask, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less. More specifically, the surfactant content in the chemical solution used in step 1 is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and even more preferably 0.1% by mass or more and 2% by mass or less.

[0029] <Solvent> In one or more embodiments, the additive contains a solvent. The solvent may be one type or a combination of two or more types. In one or more embodiments, the solvent is an organic solvent, and from the viewpoint of improving resin mask peelability, glycol ethers are preferred. From the same viewpoint, examples of glycol ethers include compounds having a structure in which ethylene glycol is added to an alcohol having 1 to 8 carbon atoms by 1 to 3 moles. Specific examples of glycol ethers include at least one selected from diethylene glycol monobutyl ether (BDG), ethylene glycol monobenzyl ether (benzyl glycol), diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether, and among these, from the same viewpoint, ethylene glycol monobenzyl ether (benzyl glycol) is preferred. From the viewpoint of improving resin mask peelability, the solvent content in the additive is preferably 3% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, and from the viewpoint of improving resin mask peelability, preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. More specifically, the solvent content in the additive is preferably 3% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less. When there is a combination of two or more solvents, the solvent content is the total content of those solvents. From the viewpoint of improving the peelability of the resin mask, the solvent content in the chemical solution used in step 1 is preferably 0.3% by mass or more, more preferably 0.6% by mass or more, and even more preferably 0.9% by mass or more, and from the viewpoint of improving the peelability of the resin mask, it is preferably 15% by mass or less, more preferably 7% by mass or less, and even more preferably 3% by mass or less. More specifically, the solvent content in the chemical solution used in step 1 is preferably 0.3% by mass or more and 15% by mass or less, more preferably 0.6% by mass or more and 7% by mass or less, and even more preferably 0.9% by mass or more and 3% by mass or less.

[0030] <Fatty Acids or Salts Thereof> In one or more embodiments, the additive may further contain fatty acids or salts thereof. The fatty acids may be linear fatty acids or branched fatty acids. The fatty acids may be saturated fatty acids or unsaturated fatty acids, but saturated fatty acids are preferred. Examples of fatty acid salts include alkali metal salts such as sodium salts and potassium salts. From the viewpoint of improving resin mask release properties and compatibility, the number of carbon atoms in the fatty acid is 8 to 10, with 8 being preferred. From the viewpoint of improving resin mask release properties and compatibility, fatty acids with 8 to 10 carbon atoms are preferred, such as caprylic acid (8 carbon atoms, linear, saturated fatty acid) and octic acid (8 carbon atoms, branched, saturated fatty acid). The content of fatty acids or their salts in the additive is preferably 3% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of improving resin mask peelability and compatibility, and preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. More specifically, the content of fatty acids or their salts in the additive is preferably 3% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less. When there is a combination of two or more fatty acids or their salts, the content of fatty acids or their salts is the total content of those. The content of fatty acids or their salts in the chemical solution used in step 1 is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, from the viewpoint of improving resin mask peelability and suppressing foaming, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. More specifically, the content of fatty acids or salts thereof in the chemical solution used in step 1 is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less, and even more preferably 0.3% by mass or more and 3% by mass or less. In one or more embodiments, the additive comprises a surfactant and a solvent, and optionally further comprises fatty acids or salts thereof.

[0031] <Other Components> In one or more embodiments, the additive may further contain other components. Examples of other components include chelating agents, inhibitors (corrosion inhibitors), thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoaming agents, and antibacterial agents.

[0032] When the additive contains a surfactant and a solvent, the mass ratio of surfactant to solvent [surfactant / solvent] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. More specifically, the mass ratio [surfactant / solvent] is preferably 0.01 or more and 1 or less, more preferably 0.05 or more and 0.5 or less, and even more preferably 0.1 or more and 0.3 or less. When the additive contains a surfactant and a fatty acid or a salt thereof, the mass ratio of surfactant to fatty acid or a salt thereof [surfactant / fatty acid or salt thereof] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.3 or less. More specifically, the mass ratio [surfactant / fatty acid or salt thereof] is preferably 0.01 or more and 1 or less, more preferably 0.05 or more and 0.5 or less, and even more preferably 0.1 or more and 0.3 or less. When the additive contains a solvent and a fatty acid or a salt thereof, the mass ratio of the solvent to the fatty acid or a salt thereof [solvent / fatty acid or salt thereof] is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 0.8 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less. More specifically, the mass ratio [solvent / fatty acid or salt thereof] is preferably 0.1 or more and 10 or less, more preferably 0.5 or more and 5 or less, and even more preferably 0.8 or more and 2 or less. When the additive contains a nonionic surfactant, the preferred range for the mass ratio of the nonionic surfactant to the solvent [nonionic surfactant / solvent] is the same range as the mass ratio [surfactant / solvent] described above. Also, the preferred range for the mass ratio of the nonionic surfactant to the fatty acid or a salt thereof [nonionic surfactant / fatty acid or salt thereof] is the same range as the mass ratio [surfactant / fatty acid or salt thereof] described above.

[0033] In one or more embodiments, the additive may be used in an aqueous solution. When the additive is used in an aqueous solution, the water content in the aqueous solution is preferably 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 15% by mass or less, in one or more embodiments. The total content of the additive components in the aqueous solution is preferably 70% by mass or more and 99% by mass or less, and more preferably 85% by mass or more and 95% by mass or less, in one or more embodiments. In one or more embodiments, the pH of the aqueous solution of the additive is preferably 6 or higher, more preferably 7 or higher and even more preferably 8 or higher, from the viewpoint of improving resin mask peelability, and preferably 13 or lower, more preferably 12.5 or lower and even more preferably 12 or lower, from the viewpoint of improving resin mask peelability and compatibility. More specifically, the pH of the aqueous solution of the additive is preferably 6 or more and 13 or lower, more preferably 7 or more and 12.5 or lower, and even more preferably 8 or more and 12 or lower.

[0034] (Water) In one or more embodiments, the chemical solution used in step 1 further contains water. Examples of water in one or more embodiments include ion-exchanged water, RO water, distilled water, pure water, ultrapure water, etc. The water content in the chemical solution used in step 1 can be the remainder after removing the alkaline agent and additives from the total amount of the chemical solution (100% by mass). For example, the water content in the chemical solution used in step 1 is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, from the viewpoint of improving the peelability of the resin mask, reducing the load on wastewater treatment, and suppressing damage to the substrate resin, and is preferably 95% by mass or less, and even more preferably 94% by mass or less. More specifically, the water content in the chemical solution used in step 1 is preferably 60% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 94% by mass or less, and even more preferably 75% by mass or more and 94% by mass or less. When the additive is used in an aqueous solution form, the water content in the chemical solution described above also includes the water content contained in the additive aqueous solution.

[0035] In this disclosure, "content of each component in the chemical solution" refers to the content of each component at the time of use, that is, at the start of use of the chemical solution for processing (resin mask peeling treatment, cleaning). In one or more embodiments, the content of each component in the chemical solution can be considered as the amount of each component blended in the chemical solution. In one or more embodiments, the content of each component in the additive can be considered as the amount of each component blended in the additive. When neutralization is involved, the blending amount and the content may differ, but they can be converted as appropriate.

[0036] The chemical solution used in step 1 may, in one or more embodiments, contain an alkaline agent other than an inorganic alkali, or it may not contain an alkaline agent other than an inorganic alkali. The chemical solution used in step 1 is, in one or more embodiments, a non-TMAH type stripping solution that does not contain tetramethylammonium hydroxide (TMAH) as an active ingredient.

[0037] (pH) In one or more embodiments, the pH of the chemical solution used in step 1 is generally 10 or higher, preferably 11 or higher, more preferably 12 or higher, from the viewpoint of improving the peelability of the resin mask, and preferably 14 or lower, from the viewpoint of suppressing damage to the substrate resin. More specifically, the pH of the chemical solution used in step 1 is preferably 10 or more and 14 or lower, more preferably 11 or more and 14 or lower, and even more preferably 12 or more and 14 or lower. The pH of the chemical solution used in step 1 is the value at 25°C and can be measured using a pH meter, specifically by the method described in the examples.

[0038] The embodiment of the chemical solution used in step 1 may be a so-called one-component type, where all components are pre-mixed and supplied to the market; a so-called two-component type, where the components are mixed at the time of use; or a form in which three or more components are mixed. For example, in one or more embodiments, the chemical solution used in step 1 may be a mixture obtained by mixing an aqueous solution containing an alkaline agent (first solution) and an aqueous solution containing an additive (second solution). The first solution and the second solution may each contain the arbitrary components mentioned above.

[0039] <Substrate to be processed> In one or more embodiments, the substrate to be processed is a substrate having a resin mask. Examples of the substrate include printed circuit boards, wafers, copper plates, aluminum plates, etc. The resin mask may be, for example, a negative-type resin mask or a positive-type resin mask, and a negative-type resin mask is preferred in terms of how easily the effects of this disclosure are exhibited. Examples of negative-type resin masks include negative-type dry film resists that have been exposed and / or developed. In this disclosure, a negative-type resin mask is formed using a negative-type resist, and for example, an exposed and / or developed negative-type resist layer is included. In this disclosure, a positive-type resin mask is formed using a positive-type resist, and for example, an exposed and / or developed positive-type resist layer is included. Examples of the thickness of the resin mask include 5 μm to 35 μm or less.

[0040] In one or more embodiments, the substrate having the resin mask (substrate to be processed) is a substrate having a metal layer and a resin mask on its surface. In one or more embodiments, the metal layer is a copper plating layer. The copper plating layer can be formed, for example, by an electrolytic copper plating method. The thickness of the metal layer is, for example, 3 μm to 30 μm. In one or more embodiments, the metal layer is used as metal wiring or wiring connection part. In one or more embodiments, the resin mask is a resin mask (resin mask layer) that exists in a perforated manner on the metal layer. In one or more embodiments, the resin mask is surrounded on its sides by the metal layer. In one or more embodiments, the shape of the resin mask layer is a polygonal (square, hexagonal, octagonal, etc.), columnar, cylindrical, or substantially cylindrical shape. The diameter of the resin mask layer (diameter of its circumscribed circle in the case of a polygon) is, for example, 20 μm to 200 μm. The thickness of the resin mask layer is, for example, 5 μm to 50 μm. Perforation ratio of the resin mask interface (μm) - ) (= Interface length between resin mask and metal layer (μm) / Area of ​​resin mask (μm) 2Examples of values ​​include 0.01 to 0.5, or 0.02 to 0.2. Here, the interface line length between the resin mask and the metal layer is, for example, the circumference of the resin mask when viewed from above. A new problem has been found with a substrate to be treated having a resin mask of this structure, in which the peelability of conventional peeling agents decreases. The chemical solution used in step 1 and the recycled chemical solution described later can suitably peel off a resin mask of this structure in one or more embodiments. In one or more embodiments, a substrate to be treated in which at least one resin mask, which exists in a perforated manner on a metal layer, is attached, as described above, is included as a substrate to be treated in one or more embodiments.

[0041] Examples of the substrate having the resin mask (substrate to be processed) include, in one or more other embodiments, electronic components and their manufacturing intermediates having a metal layer and a resin mask on their surface. Examples of electronic components include at least one component selected from printed circuit boards, wafers, copper plates, and aluminum plates. The manufacturing intermediate is an intermediate product in the manufacturing process of electronic components, and includes an intermediate product after resin mask processing. Specific examples of the substrate to be processed include, for example, electronic components on which wiring, connection terminals, etc., are formed on the substrate surface by going through a process of performing at least one of soldering and plating (copper plating, aluminum plating, nickel plating, tin plating, etc.) using a resin mask. In this disclosure, soldering means creating solder in areas on the substrate where the resin mask is not present and forming solder bumps by heating. In this disclosure, plating means performing at least one plating process selected from copper plating, aluminum plating, nickel plating, and tin plating on areas on the substrate where the resin mask is not present. The resin mask-free area refers to the portion of a resist pattern (a pattern-shaped resin mask) formed by developing a resin mask laminated onto a substrate, where the resin mask has been removed during the development process.

[0042] In one or more other embodiments, examples of the substrate having the resin mask (substrate to be processed) include a substrate having a resin mask located in a fine gap. As an example of a substrate having a resin mask located in a fine gap, after performing at least one curing treatment of exposure and development on an uncured resin mask on the substrate surface and removing the uncured resin mask, a circuit pattern is formed by plating treatment. Examples thereof include a substrate on which the circuit pattern is formed. A cured resin mask is present in the non-plated portions of the formed circuit pattern. In the present disclosure, the gap refers, in one or more embodiments, to the distance between circuit patterns (fine line portions) (the spacing between adjacent fine line portions), and is also referred to as a space (S). Examples of the thickness (plating thickness) of the fine line portion include 3 µm or more and 30 µm or less. The width of the fine line portion is also referred to as a line (L). A resin mask in a fine gap refers, in one or more embodiments, to a resin mask present in a space having a space width (S) of 50 µm or less. Examples of the thickness of the resin mask include 5 µm or more and 35 µm or less. Examples of the resin mask in a fine gap include a resin mask present in a space having a space width (S) of 5 to 25 µm.

[0043] In one or more other embodiments, the substrate to be processed is a substrate having a flux residue. In one or more embodiments, the flux residue includes a flux-derived residue remaining on a substrate after forming solder bumps using flux, and / or a substrate after soldering using flux, or the like. In one or more embodiments, examples of the substrate include a substrate having a metal surface, such as a copper plate, a steel plate, a stainless steel plate, and the like.

[0044] In one or more other embodiments, the substrate to be processed is a wafer to which a wafer processing adhesive is attached. Examples of wafer processing adhesives include at least one selected from acrylic adhesives, urethane adhesives, silicone adhesives, novolac adhesives, and polyimide adhesives. In one or more other embodiments, the wafer is a semiconductor substrate. Examples of semiconductor substrates include silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. In one or more other embodiments, the wafer is a substrate having pads and / or lands, which are areas for bonding and mounting. Examples of materials for the pads and lands include metals such as gold, copper, and aluminum.

[0045] [Step 2: Concentration Analysis] Step 2 in the substrate manufacturing method of the present disclosure is, in one or more embodiments, a step of performing acid titration of the chemical solution used in Step 1 and measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. In Step 2, the acid titration of the chemical solution is performed on alkali, and the measurement of the Brix value of the chemical solution is performed on alkali and additive.

[0046] <Measurement by Acid Titration> A titration value of the chemical solution is measured by acid titration. When the chemical solution contains an alkali hydroxide and an alkali carbonate, in one or more embodiments, the titration values for the alkali hydroxide and the alkali carbonate are measured respectively in step 2. When the alkali agent in the chemical solution used in step 1 contains an alkali hydroxide, since the chemical solution contains carbonic acid derived from carbon dioxide, the alkali hydroxide in the chemical solution may be converted into an alkali carbonate. That is, in one or more embodiments, the alkali agent in the chemical solution of step 1 contains an alkali hydroxide, and in one or more other embodiments, contains an alkali hydroxide and an alkali carbonate. Therefore, in one or more embodiments of the acid titration, an inflection point derived from the alkali hydroxide around pH 10 to 12 and an inflection point derived from the alkali carbonate at a lower pH than that are measured, and the titration values for each can be measured. From the above two titration values, the concentration of the alkali hydroxide and the concentration of the alkali carbonate in the chemical solution can be calculated. The measurement by acid titration can be performed using, for example, an automatic potentiometric titrator. Examples of the acid used for acid titration include hydrochloric acid. The titration temperature is not particularly limited and is usually normal temperature.

[0047] <Measurement of Brix Value> In the present disclosure, the Brix value of a chemical solution is a value measured using a Brix meter in one or more embodiments, and represents the concentration of active ingredients contained in the chemical solution (that is, the total concentration of the alkali agent and additives). As the Brix meter, a commercially available Brix meter such as a pocket saccharimeter can be used, for example. The Brix value measurement is preferably performed at a temperature of 25°C.

[0048] <Calculation of Additive Concentration> In one or more embodiments, the additive concentration in the chemical solution can be calculated as follows: (1) Create a calibration curve of Brix values ​​for the concentrations of alkali hydroxide, alkali carbonate, and additive. (2) Perform acid titration of the chemical solution and calculate the concentrations of alkali hydroxide and alkali carbonate in the chemical solution from the obtained titration values. (3) Measure the Brix value of the chemical solution with a Brix meter. (4) Subtract the Brix values ​​corresponding to the concentrations of alkali hydroxide and alkali carbonate from the Brix value of the chemical solution to obtain the Brix value derived from the additive in the chemical solution. Then, calculate the additive concentration in the chemical solution using the Brix value derived from the additive and the previously created calibration curve. Therefore, in one or more embodiments, the calculation of the additive concentration in step 2 includes using the concentrations of alkali hydroxide and alkali carbonate calculated from the titration values ​​of alkali hydroxide and alkali carbonate obtained by acid titration, the measured Brix value of the chemical solution, and calibration curves prepared in advance between the additive concentration and Brix value, the alkali hydroxide concentration and Brix value, and the alkali carbonate concentration and Brix value. Here, in one or more embodiments, the calculation of the additive concentration is performed by obtaining the Brix value derived from the additive by subtracting the Brix values ​​corresponding to the concentrations of alkali hydroxide and alkali carbonate from the measured Brix value of the chemical solution, and based on the Brix value derived from the additive. In one or more embodiments, the additive may be contained in the chemical solution as an aqueous solution of the additive containing a surfactant and a solvent. In one or more embodiments, the calculation of the additive concentration can be performed using a calibration curve prepared in advance that shows the relationship between the concentration of the aqueous additive solution and the Brix value.

[0049] In step 2, from the viewpoint of improving analytical reliability, it is preferable to perform the acid titration after diluting the chemical solution used in step 1 with an aqueous solvent. Therefore, in one or more embodiments, step 2 includes diluting the chemical solution used in step 1 with an aqueous solvent before the acid titration. In one or more embodiments, the acid titration is performed at 25°C on the sample after the chemical solution has been diluted with an aqueous solvent.

[0050] [Step 3] In one or more embodiments, the substrate manufacturing method of the present disclosure may further include the following Step 3. Step 3: A step of adjusting the amount (concentration) of components in the chemical solution used in Step 1 based on the concentration of the alkaline agent (alkaline hydroxide and alkaline carbonate) and the concentration of the additive obtained in Step 2 to make it the chemical solution of Step 1 or a part thereof. Here, adjusting the amount (concentration) of components in the chemical solution includes, in one or more embodiments, adjusting the concentration of the alkaline agent and / or additive in the chemical solution to make it the chemical solution for use in Step 1 or a part thereof. In one or more embodiments, the adjustment of the amount (concentration) of components in Step 3 can be done by replenishing the chemical solution used in Step 1 with chemical solution components (replenishment components) necessary for the processing in Step 1. Examples of supplementment components include the chemical solution or its components (alkaline agent, surfactant, solvent, fatty acid, water, other components, etc.) mentioned above. In one or more embodiments, the amount of supplementment component should be adjusted so that the amount of each component in the chemical solution is at a preferred content (concentration) of each component. In one or more embodiments, if the chemical solution used in step 1 is a two-part or three-part chemical, the concentration can be adjusted by replenishing each raw material solution. Methods for adjusting the concentration include, for example, mixing the chemical solution used in step 1 with an alkaline agent, mixing the chemical used in step 1 with an additive, or mixing the chemical used in step 1 with an aqueous solution containing an alkaline agent and an aqueous solution containing an additive. Known methods can be used for mixing. The mixing conditions (the mixing ratio of the chemical solution used in step 1 and the replenishment components) can be set in one or more embodiments based on the concentration of the alkaline agent (alkaline hydroxide and alkaline carbonate) and the additive obtained in step 2. In one or more embodiments, the adjustment of the component amounts in step 3 may include replenishing the alkaline agent and / or additive according to the concentration of the alkaline hydroxide, alkaline carbonate, and additive obtained in step 2.

[0051] The chemical solution after the component amounts (concentrations) have been adjusted in step 3 can be used for substrate processing in step 1. Therefore, in one or more embodiments, step 1 includes processing the substrate using the chemical solution after the component amounts (concentrations) have been adjusted in step 3 (hereinafter also referred to as "reused chemical solution"). <Reused chemical solution> In one or more embodiments, the reused chemical solution is a mixture obtained by mixing the chemical solution used in the processing of step 1 with supplementary components. The components that are blended into or included in the reused chemical solution are the same as those in the chemical solution described above. The preferred content (concentration) of each component blended into or included in the reused chemical solution is the same as the preferred content (concentration) of each component contained in the chemical solution described above.

[0052] [Concentration Analysis Method] In one embodiment, this disclosure relates to a concentration analysis method for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive does not contain quaternary ammonium hydroxide and contains a surfactant and / or a solvent, and the concentration analysis method (hereinafter also referred to as "the concentration analysis method of this disclosure") includes the steps of: acid titrating the chemical solution; measuring the Brix value of the chemical solution; and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. In the concentration analysis method of this disclosure, the method for analyzing the concentration of the additive in the chemical solution is the same analysis method as in step 2 of the substrate manufacturing method of this disclosure described above. According to the concentration analysis method of this disclosure, in addition to the concentration of the alkaline agent in the chemical solution (concentration of alkaline hydroxide and concentration of alkaline carbonate), the concentration of the additive in the chemical solution can be analyzed.

[0053] [Concentration Analyzer] In one embodiment, this disclosure relates to a concentration analyzer for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive does not contain quaternary ammonium hydroxide and contains a surfactant and / or a solvent, and the concentration analyzer (hereinafter also referred to as "the concentration analyzer of this disclosure") includes a titration unit for acid titrating the chemical solution, a Brix measurement unit for measuring the Brix value of the chemical solution, and a calculation unit for calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. In the concentration analyzer of this disclosure, the measurement method in the titration unit, the method for measuring the Brix value in the Brix measurement unit, and the method for calculating the additive concentration in the calculation unit are the same measurement and calculation methods as in step 2 of the substrate manufacturing method of this disclosure described above. In one or more embodiments, the calculation unit stores a calibration curve of concentrations and Brix values ​​of the alkaline agent and additive that has been prepared in advance. The concentration analyzer of this disclosure can analyze the concentration of alkaline agents (concentration of alkaline hydroxide and concentration of alkaline carbonate) in a chemical solution, as well as the concentration of additives in the chemical solution. The concentration analyzer of this disclosure can be suitably used, for example, in a substrate processing system as shown in Figure 1. However, Figure 1 shows one embodiment of a substrate processing system, and the components, their arrangement positions, and connection configurations do not limit the scope of the claims unless described in the claims. The substrate processing system shown in Figure 1 comprises a substrate processing apparatus 10 and the concentration analyzer 20 of this disclosure. In one or more embodiments, the substrate processing apparatus 10 comprises a chemical solution tank 11 for storing a chemical solution and a processing unit 12 for processing a substrate to be processed using the chemical solution supplied from the chemical solution tank 11. The concentration analyzer 20 of this disclosure samples the chemical solution after use in the substrate processing apparatus 10 and analyzes the concentration in the chemical solution. The concentration analyzer 20 includes a titration unit 21 for titrating a sampled drug solution, a Brix measurement unit 22 for measuring the Brix value of the sampled drug solution, and a calculation unit 23 for calculating the concentration of the additive in the drug solution using the titration value obtained by the titration unit and the Brix value obtained by the Brix measurement unit 22.In Figure 1, the titration unit 21 and the Brix measurement unit 22 are located within a single concentration analyzer, but as shown in Figure 2, they may be located in separate concentration analyzers. Also, in Figure 1, the calculation unit 23 is located within the concentration analyzer 20, but as shown in Figure 2, it may be located outside the concentration analyzer. In Figure 1, the chemical solution used in the substrate processing apparatus is sampled and its concentration is analyzed, but the chemical solution used in the substrate processing apparatus may be transferred to the concentration analyzer by a pump and its concentration analyzed thereafter.

[0054] [Method for Managing Chemical Solution] In one embodiment, this disclosure relates to a method for managing a chemical solution (hereinafter also referred to as "the management method of this disclosure") which includes a step of managing the chemical solution by analyzing the concentrations of alkaline agents and additives in the chemical solution used in the process of peeling off a resin mask using the concentration analysis method of this disclosure. In the management method of this disclosure, the chemical solution is the chemical solution used in step 1 of the substrate manufacturing method of this disclosure described above. In the management method of this disclosure, the method for analyzing the concentrations of alkaline agents and additives in the chemical solution is the same concentration analysis method as in step 2 of the substrate manufacturing method of this disclosure described above. The step of managing the chemical solution includes determining whether to replenish or replace the chemical solution based on the concentrations of alkaline agents (alkaline hydroxide and alkaline carbonate) and additives in the chemical solution. According to the management method of this disclosure, the component concentrations and degradation (lifespan) of the chemical solution can be managed using a concentration analysis method that can analyze the concentration of additives in the chemical solution in addition to the concentration of alkaline agents (concentration of alkaline hydroxide and concentration of alkaline carbonate) in the chemical solution.

[0055] [Method for Manufacturing Electronic Components] This disclosure relates to a method for manufacturing electronic components (hereinafter also referred to as "the electronic component manufacturing method of this disclosure"), which in one embodiment includes a step of analyzing the concentrations of an alkaline agent and an additive in a chemical solution used in a step of peeling off a resin mask, using the concentration analysis method of this disclosure. The chemical solution is the chemical solution used in step 1 of the substrate manufacturing method of this disclosure described above. The concentration analysis method for analyzing the concentrations of the alkaline agent and an additive in the electronic component manufacturing method of this disclosure is the same concentration analysis method as in step 2 of the substrate manufacturing method of this disclosure described above. In one or more embodiments, the electronic component manufacturing method of this disclosure includes a step of peeling off a resin mask from a substrate to be processed to which a resin mask is attached using the above-mentioned chemical solution (peeling step). Examples of substrates to be processed to which a resin mask is attached include a semiconductor substrate having metal wiring and a resin mask, a semiconductor substrate having an insulating film and a resin mask, and a semiconductor substrate having metal wiring, an insulating film and a resin mask. According to the electronic component manufacturing method of this disclosure, in addition to the concentration of alkaline agents (concentration of alkaline hydroxide and concentration of alkaline carbonate) in the chemical solution, a concentration analysis method capable of analyzing the concentration of additives in the chemical solution can be used to effectively remove resin masks attached to electronic components while controlling the component concentration and degradation (lifespan) of the chemical solution, thereby enabling the manufacture of highly reliable electronic components.

[0056] This disclosure further relates to one or more embodiments described below. <1> A method for manufacturing a substrate, comprising the following steps 1 and 2: Step 1: A step of treating a substrate with a chemical solution containing an alkaline agent and an additive. Step 2: A step of performing an acid titration of the chemical solution used in step 1 and measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value, wherein the additive includes a surfactant and / or a solvent. <2> The method for manufacturing a substrate according to <1>, further comprising the following step 3. Step 3: Based on the concentration of the alkaline agent and the concentration of the additive obtained in Step 2, the amount of components in the chemical solution used in Step 1 is adjusted to make it the chemical solution of Step 1 or a part thereof. <3> The alkaline agent in Step 1 includes an alkaline hydroxide, and the calculation of the additive concentration in Step 2 includes using the concentrations of the alkaline hydroxide and alkaline carbonate calculated from the titration values ​​of the alkaline hydroxide and alkaline carbonate obtained by acid titration, the measured Brix value of the chemical solution, and calibration curves prepared in advance between the concentration of the additive and the Brix value, the calibration curve between the concentration of the alkaline hydroxide and the Brix value, and the calibration curve between the concentration of the alkaline carbonate and the Brix value. This is the method for manufacturing a substrate according to any one of <1> to <3>. <4> In Step 2, the acid titration of the chemical solution is performed on the alkali, and the measurement of the Brix value of the chemical solution is performed on the alkali and the additive. This is the method for manufacturing a substrate according to any one of <1> to <4>. <6> The method for manufacturing a substrate according to <5>, wherein the inorganic alkali is at least one selected from alkali metal hydroxides and carbonates. <7> The method for manufacturing a substrate according to <5> or <6>, wherein the inorganic alkali is at least one selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), and potassium carbonate (K2CO3). <8> The method for manufacturing a substrate according to any one of <1> to <7>, wherein the content of the alkaline agent in the chemical solution used in step 1 is 0.5% by mass or more, or 1% by mass or more, or 2% by mass or more, and 15% by mass or less, or 12% by mass or less, or 10% by mass or less.<9> The method for manufacturing a substrate according to any one of <1> to <8>, wherein the additive contained in the chemical solution used in step 1 includes a surfactant and a solvent. <10> The method for manufacturing a substrate according to any one of <1> to <9>, wherein the surfactant is a nonionic surfactant. <11> The method for manufacturing a substrate according to <10>, wherein the nonionic surfactant is a polyoxyethylene alkyl ether. <12> The method for manufacturing a substrate according to <11>, wherein the number of carbon atoms in the alkyl group of the polyoxyethylene alkyl ether is 8 or more, or 10 or more, and 22 or less, or 20 or less. <13> The method for manufacturing a substrate according to <11> or <12>, wherein the average number of moles of ethyleneoxy groups added to the polyoxyethylene alkyl ether is 3 or more, or 4 or more, or 5 or more, and 12 or less, or 10 or less, or 9 or less. <14> The method for manufacturing a substrate according to any one of <1> to <13>, wherein the amount of surfactant in the additive is 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 50% by mass or less, or 35% by mass or less, or 20% by mass or less. <15> The method for manufacturing a substrate according to any one of <1> to <14>, wherein the amount of surfactant in the chemical solution used in step 1 is 0.01% by mass or more, or 0.05% by mass or more, or 0.1% by mass or more, and 10% by mass or less, or 5% by mass or less, or 2% by mass or less. <16> The method for manufacturing a substrate according to any one of <1> to <15>, wherein the solvent is a glycol ether. <17> The method for manufacturing a substrate according to any one of <1> to <16>, wherein the solvent is at least one selected from diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether. <18> A method for manufacturing a substrate according to any one of <1> to <17>, wherein the solvent content in the additive is 3% by mass or more, or 10% by mass or more, or 30% by mass or more, and 90% by mass or less, or 70% by mass or less, or 50% by mass or less.<19> The method for manufacturing a substrate according to any one of <1> to <18>, wherein the solvent content in the chemical solution used in step 1 is 0.3% by mass or more, or 0.6% by mass or more, or 0.9% by mass or more, and is 15% by mass or less, or 7% by mass or less, or 3% by mass or less. <20> The method for manufacturing a substrate according to any one of <1> to <19>, wherein the additive contained in the chemical solution used in step 1 further comprises a fatty acid or a salt thereof. <21> The method for manufacturing a substrate according to any one of <1> to <20>, wherein the fatty acid or salt thereof content in the additive is 3% by mass or more, or 10% by mass or more, or 20% by mass or more, and is 50% by mass or less, or 45% by mass or less, or 40% by mass or less. <22> The method for manufacturing a substrate according to any one of <1> to <21>, wherein the content of fatty acids or salts thereof in the chemical solution used in step 1 is 0.1% by mass or more, or 0.2% by mass or more, or 0.3% by mass or more, and is 10% by mass or less, or 5% by mass or less, or 3% by mass or less. <23> The method for manufacturing a substrate according to any one of <1> to <22>, wherein the additive does not contain quaternary ammonium hydroxide, or the content of quaternary ammonium hydroxide is 0.1% by mass or less. <24> The method for manufacturing a substrate according to any one of <1> to <23>, wherein the pH of the aqueous solution of the additive is 6 or more, or 7 or more, or 8 or more, and is 13 or less, or 12.5 or less, or 12 or less. <25> The method for manufacturing a substrate according to any one of <1> to <24>, wherein the substrate to be processed is a substrate having a resin mask, the chemical solution is a release agent composition for removing the resin mask, and step 1 is a step of removing the resin mask from the substrate having the resin mask using the chemical solution. <26> A concentration analysis method for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive contains a surfactant and / or a solvent, and the concentration analysis method comprises the steps of acid titrating the chemical solution, measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value.<27> A concentration analyzer for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive contains a surfactant and / or a solvent, and the concentration analyzer includes a titration unit for acid titrating the chemical solution, a Brix measurement unit for measuring the Brix value of the chemical solution, and a calculation unit for calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. <28> A method for manufacturing an electronic component, comprising the step of analyzing the concentrations of an alkaline agent and an additive in a chemical solution used in the step of peeling off a resin mask, using the concentration analysis method described in <26>. <29> A method for manufacturing a substrate, comprising the following steps 1, 2 and 3. Step 1: A step of treating a substrate with a chemical solution containing an alkaline agent and an additive. Step 2: An acid titration of the chemical solution used in Step 1 and measurement of the Brix value of the chemical solution are performed, and the concentration of the additive in the chemical solution is calculated using the obtained titration value and Brix value. Step 3: Based on the concentrations of the alkaline agent and the additive obtained in Step 2, the amount of components in the chemical solution used in Step 1 is adjusted to make it the chemical solution of Step 1 or a part thereof. However, the additive includes a nonionic surfactant and a glycol ether, the alkaline agent in Step 1 includes an alkaline hydroxide, and the calculation of the additive concentration in Step 2 includes using the concentrations of the alkaline hydroxide and alkaline carbonate calculated from the titration values ​​of the alkaline hydroxide and alkaline carbonate obtained by acid titration, the measured Brix value of the chemical solution, and calibration curves between the concentration of the additive and the Brix value, the concentration of the alkaline hydroxide and the Brix value, and the concentration of the alkaline carbonate and the Brix value that have been prepared in advance.

[0057] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited in any way by these examples.

[0058] 1. Preparation of Additive (Aqueous Solution) Sodium hydroxide (NaOH), octic acid, caprylic acid, polyoxyethylene (9) lauryl ether, benzyl glycol, and water were blended to obtain an aqueous additive solution (pH 10.1) in the composition shown in Table 1. The concentrations of each component listed in Table 1 are the active ingredient concentrations (mass%) calculated from the blending amounts.

[0059] The following substances were used to prepare the additive aqueous solution: NaOH: sodium hydroxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (NaOH forms salts with fatty acids in aqueous solution) Octylic acid [manufactured by KH Neochem Co., Ltd.] (fatty acid) Caprylic acid [manufactured by Kao Corporation] (fatty acid) Polyoxyethylene (9) lauryl ether [manufactured by Kao Corporation] (surfactant) Benzyl glycol [manufactured by Nippon Emulsifier Co., Ltd.] (solvent) Water [pure water with an electrical conductivity of 1 μS / cm or less, produced using Organo's G-10DSTSET pure water system]

[0060]

[0061] Furthermore, the obtained additive aqueous solution can be considered to contain 8% by mass of surfactant (polyoxyethylene (9) lauryl ether), 39% by mass of fatty acid salts (sodium salts of octic acid and caprylic acid), 40% by mass of solvent (benzyl glycol), and 13% by mass of water.

[0062] 2. Preparation of Compositions (Solutions) for Examples 1-2 and Comparative Example 1 Sodium hydroxide (NaOH), sodium carbonate (Na2CO3), the additive aqueous solutions shown in Table 1, and water were blended to obtain the compositions (solutions) for Examples 1-2 and Comparative Example 1. The concentrations of each component listed in Table 2 are the active ingredient concentrations (mass%) calculated from the blending amounts. The water blending amounts shown in Table 2 do not include the water contained in the additive aqueous solutions. The following were used to prepare the compositions (solutions): Sodium hydroxide [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (alkaline agent) Sodium carbonate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (alkaline agent) Water [pure water with an electrical conductivity of 1 μS / cm or less, produced using an Organo pure water system G-10DSTSET]

[0063] [pH Measurement] The pH of the composition (chemical solution) at 25°C was measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and the value was obtained 3 minutes after immersing the pH meter electrode in the composition. The results are shown in Table 2. The pH of the additive aqueous solution was measured in the same manner.

[0064] 3. Analytical Method [Examples 1-2: Concentration Analysis Using Titration and Brix Measurement] First, a calibration curve of Brix values ​​for the concentrations of aqueous solutions of sodium hydroxide (NaOH), aqueous solution of sodium carbonate (Na2CO3), and the additive aqueous solution prepared in 1 above was created using a pocket refractometer (ATAGO, PAL-BX / RI). The Brix values ​​of each composition (chemical solution) prepared in 2 above were also measured using a pocket refractometer (ATAGO, PAL-BX / RI) (Brix measurement temperature: 25°C). Next, each composition (chemical solution) prepared in 2 above was titrated using a potentiometric automatic titrator (Kyoto Electronics Manufacturing Co., Ltd., AT-710) with a sample amount of 5 g each, using water (45 g) as the dilution solvent (dilution ratio: 10 times) (titration temperature: 25°C). A titration curve showing the relationship between the amount of acid added by titration and pH was obtained, and two inflection points were detected, appearing at pH 12-10 (inflection point due to alkali hydroxide) and pH 9-7 (inflection point due to alkali carbonate). The acid used in the titration was hydrochloric acid [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 0.5 mol / L aqueous solution]. The concentrations of sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) were calculated for each composition (chemical solution) using the following formulas. NaOH (%) = Titration volume at the inflection point for pH 12-10 (mL) ÷ 1000 × Titrating hydrochloric acid concentration (mol / L) × Molecular weight of NaOH ÷ 5 × 100 Na2CO3 (%) = (Titration volume at the inflection point for pH 9-7 (mL) - Titration volume at the inflection point for pH 12-10 (mL)) ÷ 1000 × Titrating hydrochloric acid concentration (mol / L) × Molecular weight of Na2CO3 ÷ 5 × 100 Finally, the Brix values ​​corresponding to sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) were subtracted from the Brix values ​​of each composition (chemical solution) to determine the Brix values ​​derived from the additive aqueous solutions prepared in step 1 above. Based on the calibration curve of additive aqueous solution concentration and Brix value, the concentration of the additive aqueous solution in each composition (chemical solution) was determined. The results are shown in Table 2.

[0065] [Comparative Example 1: Concentration Analysis by Titration Only] The compositions (chemical solutions) of Comparative Example 1 prepared in step 2 above were titrated using a potentiometric automatic titrator (Kyoto Electronics Manufacturing Co., Ltd., AT-710) with each sample amount set to 5 g, using water (45 g) as the dilution solvent (dilution ratio: 10 times) (titration temperature: 25°C). A titration curve showing the relationship between the amount of acid added by titration and pH was obtained, and two inflection points were detected that appeared at pH 12-10 (inflection point due to alkali hydroxide) and 9-7 (inflection point due to alkali carbonate). The acid used in the titration was hydrochloric acid [Fujifilm Wako Pure Chemical Industries, Ltd., 0.5 mol / L aqueous solution]. The concentrations of sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) were calculated using the following formulas. However, it was not possible to determine the concentration of the additive aqueous solution in each composition (chemical solution).

[0066]

[0067] As shown in Table 2, in Examples 1 and 2, which used an analytical method combining Brix measurement and titration, the concentrations of the alkaline agent and the additive aqueous solution could be measured. On the other hand, in Comparative Example 1, which used an analytical method using titration only, the concentration of the alkaline agent could be measured, but the concentration of the additive aqueous solution could not.

[0068] This disclosure provides a method for manufacturing a substrate that includes an analytical step capable of analyzing the concentrations of alkaline agents and additives in a chemical solution, a concentration analysis method and concentration analysis apparatus capable of analyzing the concentrations of alkaline agents and additives in a chemical solution, and a method for manufacturing electronic components using the concentration analysis method. By using the substrate manufacturing method of this disclosure, it is possible to improve the performance and reliability of the manufactured electronic components and improve the productivity of semiconductor devices.

[0069] 10: Substrate processing device, 11: Chemical solution tank, 12: Processing unit, 20: Concentration analyzer, 20a: Concentration analyzer a, 20b: Concentration analyzer b, 21: Titration unit, 22: Brix measurement unit, 23: Calculation unit

Claims

1. A method for manufacturing a substrate, comprising the following steps 1 and 2: Step 1: A step of treating a substrate with a chemical solution containing an alkaline agent and an additive. Step 2: A step of performing an acid titration of the chemical solution used in step 1 and measuring the Brix value of the chemical solution, and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value. However, the additive includes a surfactant and / or a solvent.

2. A method for manufacturing a substrate according to claim 1, further comprising step 3 below: Step 3: A step of adjusting the amount of components in the chemical solution used in step 1 based on the concentration of the alkaline agent and the concentration of the additive obtained in step 2 to obtain the chemical solution of step 1 or a part thereof.

3. The method for manufacturing a substrate according to claim 1 or 2, wherein the alkaline agent in step 1 includes an alkaline hydroxide, and the calculation of the additive concentration in step 2 is performed using the concentrations of the alkaline hydroxide and alkaline carbonate calculated from the titration values ​​of the alkaline hydroxide and alkaline carbonate obtained by acid titration, the measured Brix value of the chemical solution, and calibration curves prepared in advance between the concentration of the additive and the Brix value, the concentration of the alkaline hydroxide and the Brix value, and the concentration of the alkaline carbonate and the Brix value.

4. A method for manufacturing a substrate according to any one of claims 1 to 3, wherein in step 2, the acid titration of the chemical solution is performed on the alkali, and the Brix value of the chemical solution is measured on the alkali and the additive.

5. The method for manufacturing a substrate according to any one of claims 1 to 4, wherein the alkaline agent contained in the chemical solution used in step 1 includes an inorganic alkali.

6. The method for manufacturing a substrate according to claim 5, wherein the inorganic alkali is at least one selected from alkali metal hydroxides and carbonates.

7. The method for manufacturing a substrate according to claim 5 or 6, wherein the inorganic alkali is at least one selected from sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), and potassium carbonate (K2CO3).

8. The method for manufacturing a substrate according to any one of claims 1 to 7, wherein the content of the alkaline agent in the chemical solution used in step 1 is 0.5% by mass or more and 15% by mass or less.

9. The method for manufacturing a substrate according to any one of claims 1 to 8, wherein the additives contained in the chemical solution used in step 1 include a surfactant and a solvent.

10. The method for manufacturing a substrate according to any one of claims 1 to 9, wherein the surfactant is a nonionic surfactant.

11. The method for producing a substrate according to claim 10, wherein the nonionic surfactant is a polyoxyethylene alkyl ether.

12. The method for manufacturing a substrate according to any one of claims 1 to 11, wherein the solvent is a glycol ether.

13. The method for manufacturing a substrate according to any one of claims 1 to 12, wherein the additive contained in the chemical solution used in step 1 further comprises a fatty acid or a salt thereof.

14. The method for manufacturing a substrate according to any one of claims 1 to 13, wherein the additive does not contain quaternary ammonium hydroxide, or the content of quaternary ammonium hydroxide is 0.1% by mass or less.

15. The method for manufacturing a substrate according to any one of claims 1 to 14, wherein the substrate to be processed is a substrate having a resin mask, the chemical solution is a release agent composition for removing the resin mask, and step 1 is a step of removing the resin mask from the substrate having the resin mask using the chemical solution.

16. A concentration analysis method for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive contains a surfactant and / or a solvent, and the method comprises the steps of: acid titrating the chemical solution; measuring the Brix value of the chemical solution; and calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value.

17. A concentration analyzer for analyzing the concentrations of an alkaline agent and an additive in a chemical solution, wherein the chemical solution contains an alkaline agent and an additive, the additive contains a surfactant and / or a solvent, and the concentration analyzer includes a titration unit for acid titrating the chemical solution, a Brix measurement unit for measuring the Brix value of the chemical solution, and a calculation unit for calculating the concentration of the additive in the chemical solution using the obtained titration value and Brix value.

18. A method for manufacturing an electronic component, comprising the step of analyzing the concentrations of an alkaline agent and an additive in a chemical solution used in the step of peeling off a resin mask, using the concentration analysis method described in claim 16.

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