Release agent, solvent for semiconductor, treatment liquid for semiconductor, release method, and semiconductor device manufacturing method

Abstract

A release agent used to release a resin having an ether bond from a substrate, the agent comprising a sulfonic acid, a release promoter catalyst, and water.

Description

Stripping agent, semiconductor solvent, semiconductor processing solution, stripping method, and semiconductor element manufacturing method

[0001] The present invention relates to a stripping agent for a resin having an ether bond, a semiconductor solvent, a semiconductor processing liquid, and a stripping method, and also to a method for manufacturing a semiconductor element using these.

[0002] In recent years, semiconductor elements have become increasingly sophisticated and highly integrated. Various resins are used in semiconductors for a variety of purposes. Examples of resins used in semiconductors include epoxy resins, phenolic resins, silicone resins, and acrylic resins for semiconductor encapsulation, and epoxy resins, urethane resins, silicone resins, and polyimide resins for conductive adhesives.

[0003] Forming semiconductor devices using these resins involves processing and removing the resin after molding. Many of these resins have high chemical resistance, making the technology for removing them from semiconductor substrates increasingly important. For example, epoxy resins after thermal curing have a three-dimensional network structure and excellent chemical resistance. The chemical resistance of epoxy resins varies primarily depending on the curing agent, with typical curing agents typically being amines or acid anhydrides. Chemical methods for removing the structures formed by these curing agents involve attacking the C-N bonds in amine-curing types and the ester bonds in acid anhydride-curing types.

[0004] Patent Document 1 describes a treatment liquid for a carbon material / acid anhydride-cured epoxy resin composite material, which is characterized by containing an alkali metal compound and a monoalcohol, and a separation method using the same.

[0005] Patent Document 2 describes a method for treating a composite material of inorganic material / cured epoxy resin, which is characterized by containing a catalyst for decomposing a cured epoxy resin and an organic solvent.

[0006] JP 2005-255899 A JP 2007-297641 A

[0007] Some epoxy resins are crosslinked by acids, lack highly chemically active bonds such as ester bonds, and have a three-dimensional structure formed by ether bonds. Patent Document 1 proposes a treatment solution containing an alkali metal compound and monoalcohols. The epoxy resin to be treated in this invention is an acid anhydride-cured epoxy resin, and its decomposition is thought to be due to transesterification and alcoholysis. Therefore, the inventors' investigations have revealed that removal efficiency is significantly reduced in the case of epoxy resins that have ether bonds and no ester crosslinks.

[0008] Furthermore, Patent Document 2 proposes a method of cleaving ether bonds using a cured epoxy resin decomposition catalyst. In this invention, it is stated that the cured epoxy resin to be treated preferably contains a halogen atom. It has been revealed that the removal efficiency is significantly reduced when used with an epoxy resin having a normal ether bond, in which the ortho-position of the benzene ring to which the ether group is bonded is not substituted with a halogen atom. Furthermore, when used in semiconductor devices, epoxy resins are sometimes used as adhesives between silicon wafers. However, the inventors' investigations have revealed that, because silicon reacts and corrodes under basic conditions, the use of the treatment solution described in Patent Document 2 can cause roughening of the Si substrate depending on the cured epoxy resin decomposition catalyst used.

[0009] Therefore, an object of the present invention is to provide a stripping agent (hereinafter referred to as stripping agent) that can efficiently strip a resin having an ether bond from a substrate at a high speed. Also, in the semiconductor field, an object of the present invention is to provide a semiconductor solvent (hereinafter also referred to as solvent), a semiconductor treatment liquid (hereinafter also referred to as treatment liquid), a stripping method, and a semiconductor device manufacturing method that can suppress corrosion of Si in a substrate when a resin having an ether bond contained in a semiconductor wafer is stripped from the substrate.

[0010] The present inventors have conducted extensive research to solve the above problems and have found that resins having ether bonds can be rapidly stripped, dissolved, or treated from a substrate by using a stripping agent, solvent, or treatment liquid containing a stripping-promoting catalyst, sulfonic acid, and water, which has led to the completion of the present invention.

[0011] That is, the present invention is configured as follows. Item 1: A stripping agent used to strip a resin having an ether bond from a substrate, the stripping agent comprising a sulfonic acid, a stripping-promoting catalyst, and water. Item 2: The stripping agent according to Item 1, wherein the stripping-promoting catalyst is at least one selected from the group consisting of an oxidizing agent and an acid catalyst. Item 3: The stripping agent according to Item 2, wherein the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, a halogen oxygen acid, a hydrohalic acid, a halogen, and ozone. Item 4: The stripping agent according to Item 3, wherein the halogen oxygen acid is at least one selected from the group consisting of orthoperiodic acid and an orthoperiodate ion. Item 5: The stripping agent according to any one of Items 2 to 4, wherein the acid catalyst is at least one selected from the group consisting of hydrogen halide, sulfuric acid, nitric acid, and nitrous acid. Item 6: The stripping agent according to any one of Items 1 to 5, wherein the resin having an ether bond is an epoxy resin. Item 7: The stripping agent according to any one of Items 1 to 6, wherein the stripping agent is for semiconductors. Item 8: A method for stripping a resin having an ether bond from a semiconductor substrate, comprising contacting the resin having an ether bond with the stripping agent according to Item 7 at a temperature of 20°C or higher and 200°C or lower. Item 9: A method for manufacturing a semiconductor element, comprising a step of performing stripping by the stripping method according to Item 8. Item 10: A semiconductor solvent used to dissolve a resin having an ether bond and strip it from a semiconductor substrate, the semiconductor solvent comprising sulfonic acid, a stripping-promoting catalyst, and water. Item 11: A semiconductor treatment liquid used to strip a resin having an ether bond from a semiconductor substrate, the semiconductor treatment liquid comprising sulfonic acid, a stripping-promoting catalyst, and water. Item 12: A method for manufacturing a semiconductor element, comprising a stripping step of performing a treatment to strip a resin having an ether bond from a semiconductor substrate using the semiconductor solvent according to Item 10 or the semiconductor treatment liquid according to Item 11, the treatment being carried out at 20°C or higher and 200°C or lower.

[0012] By using the stripping agent, solvent, or treatment liquid of the present invention, it is possible to rapidly strip a resin having an ether bond from a substrate and effectively dissolve (high solubility) or treat it. Furthermore, when the stripping agent, solvent, or treatment liquid of the present invention is used for semiconductor applications, in addition to the above-mentioned effects, it is possible to maintain good smoothness of the Si surface after treatment, and it is possible to prevent a decrease in reliability in the production of semiconductor elements.

[0013] The present invention will be described in detail below. The following description is an example (typical example) of the present invention, and the present invention is not limited thereto. Furthermore, the present invention can be implemented with any modifications within the scope of the gist thereof.

[0014] In this specification, a numerical range expressed using "to" means "greater than or equal to," and refers to a range that includes the numerical values ​​before and after "to" as the lower and upper limits. Furthermore, in this specification, the expression "A or B" can be interpreted as "at least one selected from the group consisting of A and B." Furthermore, although multiple embodiments are described in this specification, various conditions in each embodiment can be applied to each other to the extent applicable. Furthermore, when describing component C contained in a stripper, solvent, or treatment liquid as "component C contains D," this can be interpreted as "the stripper, solvent, or treatment liquid contains at least D as component C." Furthermore, in this specification, "concentration" refers to the content of each component in a solution. Therefore, "concentration" can express not only the content of a solute in a solution, but also the content of a solvent, such as water, in a solution.

[0015] (Removal Agent) In the release agent according to one embodiment of the present invention, the release agent for resins having ether bonds (hereinafter referred to as release agent) refers to a chemical solution that removes resins having ether bonds from a substrate, and is characterized by containing a release-promoting catalyst and sulfonic acid. In the semiconductor field, the release agent also refers to a chemical solution that removes resins having ether bonds contained in semiconductor wafers from a substrate. This release agent encompasses, for example, cases where an adhesive layer between a substrate and a resin is removed, or where a portion of a resin is removed from a resin layer. Therefore, the release agent according to this embodiment can be suitably used in each semiconductor manufacturing process in the semiconductor field.

[0016] (Semiconductor Solvent) The chemical solution (removal agent) according to this embodiment acts not only on the interface between the substrate and the resin having an ether bond but also on the ether bond within the resin molecule, and can therefore dissolve the resin by cleaving the ether bond. Therefore, the chemical solution according to this embodiment can also be used as a semiconductor solvent that dissolves a resin having an ether bond (dissolves a resin whose ether bond has been cleaved) and is used to remove the resin from a semiconductor substrate.

[0017] (Semiconductor Treatment Solution) As described above, the chemical solution (stripper) according to this embodiment can be used as a semiconductor stripper (hereinafter referred to as a semiconductor stripper) that strips a resin having an ether bond from a semiconductor substrate, or as a semiconductor solvent (hereinafter referred to as a semiconductor solvent) that dissolves a resin having an ether bond. In addition, the chemical solution according to this embodiment is unlikely to corrode Si used as a substrate, and the smoothness of the Si is unlikely to be impaired by the chemical solution. Therefore, the chemical solution according to this embodiment can also be used as a semiconductor treatment solution used to strip a resin having an ether bond from a semiconductor substrate. Note that, within the applicable range, the expressions "stripping," "removal," and "dissolution" can be used interchangeably.

[0018] The chemical solution (stripper, solvent, or treatment solution) will be specifically described below. As described above, these are characterized by containing sulfonic acid, and may contain any components other than sulfonic acid. However, from the viewpoint of efficient stripping, a configuration containing sulfonic acid, a stripping-promoting catalyst, and water is particularly preferred. However, the chemical solution according to this embodiment is not limited to these configurations.

[0019] (Acids Having a Sulfonic Acid Group (Sulfonic Acid)) Examples of acids having a sulfonic acid group (hereinafter also referred to as sulfonic acids) contained in the stripping agent, solvent, or treatment solution include methanesulfonic acid, methanedisulfonic acid, aminomethanesulfonic acid, ethanesulfonic acid, 1,2-ethanedisulfonic acid, propanesulfonic acid, butanesulfonic acid, hexanesulfonic acid, benzenesulfonic acid, o-benzenedisulfonic acid, m-benzenedisulfonic acid, p-benzenedisulfonic acid, 1,3,5-benzenetrisulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid, 1,6-naphthalenedisulfonic acid, o-tolyltrisulfonic acid, 2-naphthalenesulfonic acid, 1,6-naphthalenedisulfonic acid, 2-methyl-2-propanol ... Examples of suitable sulfonic acids include methanesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, o-phenolsulfonic acid, m-phenolsulfonic acid, p-phenolsulfonic acid, o-nitrobenzenesulfonic acid, m-nitrobenzenesulfonic acid, p-nitrobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, o-sulfobenzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, trifluoromethanesulfonic acid, sulfoacetic acid, 5-sulfosalicylic acid, and amidosulfonic acid. Among these, from the viewpoint of the efficiency of removing resins having ether bonds, solutions containing methanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, m-nitrobenzenesulfonic acid, and trifluoromethanesulfonic acid are preferred. Furthermore, the sulfonic acid contained in the stripper, solvent, and treatment solution may be contained in a free state, or in a dissociated ion state, particularly in a state of forming a salt with another cation. The sulfonic acid may be contained in one kind or in two or more kinds. For example, by containing multiple kinds of sulfonic acids, such as o-toluenesulfonic acid and p-toluenesulfonic acid, resins having ether bonds may be efficiently removed.

[0020] The sulfonic acid in the stripping agent, solvent, or treatment solution may contain water, and the sulfonic acid concentration may be any concentration that can strip and remove part or all of the resin having an ether bond from the substrate. The concentration of sulfonic acid in the stripping agent, solvent, or treatment solution can be appropriately adjusted taking into account the type of stripping-promoting catalyst or sulfonic acid used, the type of resin contained in the semiconductor element, resin properties such as chemical resistance, amount present, location present, type of functional group, and glass transition temperature, as well as treatment conditions such as stripping. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of sulfonic acid in the aqueous sulfonic acid solution is preferably 0.001 wt% to 99.999 wt%, more preferably 0.01 wt% to 99.9 wt%, even more preferably 0.1 wt% to 99.0 wt%, and most preferably 0.5 wt% to 99.0 wt%. The above-mentioned concentrations of each sulfonic acid may be the concentrations of sulfonic acid in the stripping agent, solvent, or treatment liquid, or may be the concentrations of sulfonic acid used as a raw material, regardless of the type of sulfonic acid, etc. Preferred ranges according to the type of sulfonic acid and the type of stripping-promoting catalyst will be described below in more detail, but these concentrations refer to the concentrations of sulfonic acid in the stripping agent, solvent, or treatment liquid.

[0021] When methanesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of the sulfonic acid can be appropriately adjusted taking into consideration the resin properties such as the type of resin contained in the semiconductor element, chemical resistance, amount present, location present, type of functional group, and glass transition temperature, as well as the conditions of treatment such as stripping. From the viewpoint of the removal efficiency of resins having ether bonds, the concentration of the sulfonic acid is preferably 0.5 wt% to 99.9 wt%, more preferably 1.5 wt% to 99.0 wt%, and even more preferably 4.0 wt% to 99.0 wt%, and from the viewpoints of economy and handling safety, 80.0 wt% to 99.0 wt% is most preferred.

[0022] When p-toluenesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of the sulfonic acid can be appropriately adjusted taking into consideration resin properties such as the type of resin contained in the semiconductor element, chemical resistance, amount present, location present, type of functional group, and glass transition temperature, as well as treatment conditions such as stripping. From the viewpoint of the removal efficiency of resins having ether bonds, the concentration of the sulfonic acid is preferably 0.001 wt % to 50.0 wt %, more preferably 0.01 wt % to 40.0 wt %, and even more preferably 0.1 wt % to 30.0 wt %, and from the viewpoints of economy and handling safety, 0.5 wt % to 15.0 wt % is most preferred.

[0023] When methanesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the peel-promoting catalyst, the concentration range of the sulfonic acid can be appropriately adjusted taking into consideration the resin properties such as the type of resin contained in the semiconductor element, chemical resistance, amount present, location of presence, type of functional group, and glass transition temperature, as well as the conditions of treatment such as peeling. From the viewpoint of the removal efficiency of resins having ether bonds, the concentration of the sulfonic acid is preferably 10.0 wt% to 99.999 wt%, more preferably 37.0 wt% to 99.9 wt%, and even more preferably 50.0 wt% to 98.0 wt%, and from the viewpoint of economy and handling safety, 60.0 wt% to 95.0 wt% is most preferred. When p-toluenesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the peel-promoting catalyst, the concentration range of the sulfonic acid can be appropriately adjusted taking into consideration the resin properties such as the type of resin contained in the semiconductor element, chemical resistance, amount present, location of presence, type of functional group, and glass transition temperature, as well as the conditions of treatment such as peeling. From the viewpoint of the efficiency of removing resins having ether bonds, the concentration of sulfonic acid is preferably 0.001 wt % or more and 99.999 wt % or less, more preferably 0.1 wt % or more and 98.0 wt % or less, and even more preferably 16.0 wt % or more and 92.0 wt % or less, and from the viewpoint of economy and safety in handling, it is most preferably 55.0 wt % or more and 85.0 wt % or less.

[0024] Furthermore, when using an aqueous sulfonic acid solution, the sulfonic acid may be produced by removing water from the sulfonic acid. Examples of such a procedure include heating the sulfonic acid to remove water; ２ O ５ Or P ４ O １０ Examples of such a method include adding a dehydrating agent such as phosphoric anhydride to sulfonic acid. By adding such a water-removing operation, the concentration of sulfonic acid can be adjusted. These operations may be performed individually or in combination. Combining multiple operations may allow the water content in sulfonic acid to be removed with good reproducibility.

[0025] The sulfonic acid contained in the stripping agent, solvent, or treatment liquid, or the ions generated by dissociation of the sulfonic acid, is preferably a sulfonic acid from which metal ions, organic impurities, and / or particle particles have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, various purification treatments, or the like.

[0026] The treatment time using a stripping agent, solvent, or treatment solution may be any time that allows for the partial or complete removal of the resin having an ether bond from the substrate, and may be adjusted appropriately taking into consideration the type, chemical resistance, amount present, location of the resin, type of functional group, resin properties, and the type of stripping agent, solvent, or treatment solution contained in the semiconductor element. From the viewpoint of the removal efficiency of the resin having an ether bond, the treatment time is preferably 0.1 minutes to 100 hours, more preferably 0.1 minutes to 50 hours, and even more preferably 0.1 minutes to 15 hours, and most preferably 0.1 minutes to 90 minutes from the viewpoint of economic efficiency. The treatment temperature using a stripping agent, solvent, or treatment solution may be any time that allows for the partial or complete removal of the resin having an ether bond from the semiconductor substrate, and may be adjusted appropriately taking into consideration the type, chemical resistance, amount present, location of the resin, type of functional group, resin properties, type of stripping-promoting catalyst, amount added, or type of sulfonic acid contained in the semiconductor element. From the viewpoint of the efficiency of removing the resin having an ether bond, the treatment temperature is preferably from 20° C. to 400° C., more preferably from 20° C. to 350° C., even more preferably from 20° C. to 200° C., and from the viewpoint of safety in handling, most preferably from 50° C. to 160° C. If the temperature is within the above range, the resin having an ether bond can be efficiently removed at a high peeling rate.

[0027] The environment in which the stripping agent, solvent, or treatment solution is used is not particularly limited, and may be in the air or in an inert gas such as nitrogen or argon. The treatment may be performed under normal pressure, reduced pressure, or increased pressure. From the viewpoint of safety during treatment, treatment under normal pressure is preferred.

[0028] The treatment method with the stripping agent, solvent, or treatment liquid is not particularly limited, and the object may be immersed in the stripping agent, solvent, or treatment liquid, or the stripping agent may be sprayed onto the object using a single-wafer cleaning machine or a spray, etc. Furthermore, when treating at high temperatures, a cooler or the like may be attached during treatment, or the treatment may be performed under reflux in order to prevent volatilization of water, the stripping-promoting catalyst, etc.

[0029] The conditions for the above-described treatments can also be applied to the conditions for treatments such as peeling in the peeling method and the manufacturing method of semiconductor elements, which will be described later.

[0030] (Strip-Promoting Catalyst) The stripping agent, solvent, or treatment liquid according to this embodiment contains a strip-promoting catalyst. By including this strip-promoting catalyst, the stripping and removal of the resin having an ether bond from the substrate is promoted, the efficiency of stripping the target object from the substrate is increased, and the time required for semiconductor manufacturing can be reduced. Furthermore, by including these strip-promoting catalysts, the treatment temperature can be lowered, which is desirable from the viewpoint of safety in handling.

[0031] The stripping-promoting catalyst that can be contained in the stripper, solvent, or treatment solution may be any catalyst that can act on ether bonds within resin molecules, hydrogen bonds and ether bonds with the substrate, or adhesive layers, and may be a metal catalyst or a non-metal catalyst. Among these, non-metal catalysts are preferred from the viewpoint of not containing metal atoms that are problematic in semiconductor manufacturing, and examples of such catalysts include at least one selected from the group consisting of acid catalysts and oxidizing agents. The use of such non-metal catalysts is preferred because they avoid corrosion of the Si used in the substrate and are less likely to react with the sulfonic acid contained in the stripper, solvent, or treatment solution. Furthermore, from the viewpoint of suppressing corrosion of the Si substrate, it is preferable that the stripper, solvent, or treatment solution does not contain a basic component.

[0032] Examples of the acid catalyst include Lewis acids, inorganic acids, and organic acids. Examples of the non-metallic Lewis acids include BBr ３ bromides such as BF ３ , or PF ５Examples of suitable non-metallic catalyst inorganic acids include at least one selected from the group consisting of hydrogen halides, sulfuric acid, nitric acid, nitrous acid, orthophosphoric acid, pyrophosphoric acid, and phosphoric anhydride. Examples of suitable non-metallic catalyst organic acids include carboxylic acids such as formic acid and acetic acid. Among these, at least one selected from the group consisting of hydrogen halides, sulfuric acid, nitric acid, nitrous acid, orthophosphoric acid, and pyrophosphoric acid is preferred, at least one selected from the group consisting of hydrogen halides, sulfuric acid, nitric acid, and nitrous acid is more preferred, and nitric acid is most preferred. Note that, in this specification, the term "acid catalyst" does not include sulfonic acids.

[0033] The oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, halogen oxygen acid, hydrohalic acid, halogen, ozone, etc. Among these peel-promoting catalysts, at least one selected from the group consisting of hydrogen peroxide, hydrohalic acid, halogen oxygen acid, and ozone is preferred because it has a strong effect of cleaving ether bonds, and hydrogen peroxide is more preferred. The inventors speculate that hydrogen peroxide functions as an oxidizing agent in the composition according to this embodiment.

[0034] These exfoliation-promoting catalysts may also contain water.

[0035] (Concentration of peel-promoting catalyst) The concentration range of the peel-promoting catalyst may be any concentration range that can peel and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type of peel-promoting catalyst or sulfonic acid used, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, peeling efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of the peel-promoting catalyst in the stripping agent, solvent, or treatment liquid is preferably 0.001 wt % or more and 90 wt % or less, more preferably 0.1 wt % or more and 80 wt % or less, and even more preferably 0.7 wt % or more and 70 wt % or less, and from the viewpoint of economy and handling safety, it is most preferably 1.0 wt % or more and 70 wt % or less. When methanesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of nitric acid in the stripper, solvent, or treatment solution may be any concentration range that can strip and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of nitric acid in the stripper, solvent, or treatment solution is preferably 0.1 wt % to 80.0 wt %, more preferably 0.7 wt % to 69.0 wt %, and even more preferably 1.0 wt % to 67.0 wt %, and from the viewpoints of economy and handling safety, 1.0 wt % to 15.0 wt % is most preferred. When p-toluenesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of nitric acid in the stripper, solvent, or treatment solution may be any concentration range that can strip and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of nitric acid in the stripper, solvent, or treatment solution is preferably 30.0 wt % to 80.0 wt %, more preferably 45.0 wt % to 70.0 wt %, and even more preferably 49.0 wt % to 70.0 wt %, and from the viewpoints of economy and handling safety, 58.0 wt % to 69.5 wt % is most preferred.

[0036] When methanesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the stripping-promoting catalyst, the concentration range of hydrogen peroxide in the stripper, solvent, or treatment solution may be any concentration range that allows for the partial or complete stripping and removal of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of hydrogen peroxide in the stripper, solvent, or treatment solution is preferably 0.001 wt % to 50.0 wt %, more preferably 0.1 wt % to 20.0 wt %, and even more preferably 1.0 wt % to 15.0 wt %, and from the viewpoints of economy and handling safety, 1.5 wt % to 12.0 wt % is most preferred. When p-toluenesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the stripping-promoting catalyst, the concentration range of hydrogen peroxide in the stripping agent, solvent, or treatment solution may be any concentration range that allows for the partial or complete stripping and removal of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of hydrogen peroxide in the stripping agent, solvent, or treatment solution is preferably 0.1 wt % to 50.0 wt %, more preferably 1.0 wt % to 30.0 wt %, and even more preferably 2.5 wt % to 25.0 wt %, and from the viewpoints of economy and handling safety, 5.0 wt % to 12.5 wt % is most preferred.

[0037] (Hydrogen Halide) The type of hydrogen halide that can be used as the peel-off promoting catalyst is not particularly limited, and examples thereof include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, or ions thereof. Among these, hydrogen bromide is preferred because of its strong acidity, stability, and suitability for semiconductor applications.

[0038] (Hydrogen halide acid) The type of hydrohalogen acid that can be used as a peel-off promoting catalyst is not particularly limited, and examples thereof include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, etc. Among these, hydrobromic acid is preferred because of its strong acidity, stability, and suitability for semiconductor applications.

[0039] (Halogen Oxygen Acid) The type of halogen oxygen acid that can be used as a peeling-promoting catalyst is not particularly limited, and can be exemplified by hypochlorous acid, chlorous acid, chloric acid, perchloric acid, hypobromous acid, bromous acid, bromic acid, perbromic acid, hypoiodous acid, iodous acid, iodic acid, metaperiodic acid, or orthoperiodic acid, or their ions.Among these, hypochlorous acid, perchloric acid, hypobromous acid, or orthoperiodic acid, or their ions, are preferred because of their oxidizing power, stability, and suitability for semiconductor applications, and at least one selected from the group consisting of orthoperiodic acid and orthoperiodic acid ion is most preferred.

[0040] (Halogen) The type of halogen that can be used as the peel-promoting catalyst is not particularly limited, and examples thereof include chlorine, bromine, iodine, etc. Among these, chlorine or bromine is preferred because of its oxidizing power, stability, and suitability for semiconductor applications.

[0041] The method for adding the peel-promoting catalyst is not particularly limited and may be determined taking into consideration the type of catalyst used, etc. For example, the peel-promoting catalyst may be added by dissolving it in sulfonic acid or by dissolving sulfonic acid in a solution containing the peel-promoting catalyst. The method for dissolving the peel-promoting catalyst in sulfonic acid is not particularly limited and may be determined taking into consideration the properties of the peel-promoting catalyst, etc. The peel-promoting catalyst may be added to sulfonic acid and dissolved and mixed, or a solution containing the peel-promoting catalyst may be added to sulfonic acid and mixed. The method for dissolving sulfonic acid in a solution containing the peel-promoting catalyst is not particularly limited and may be determined taking into consideration the properties of the peel-promoting catalyst, etc. The sulfonic acid may be added to a solution containing the peel-promoting catalyst and dissolved and mixed, or a solution containing sulfonic acid may be added to a solution containing the peel-promoting catalyst and mixed. Furthermore, stirring, heating, etc. may be performed as needed. Furthermore, the peel-promoting catalyst only needs to be partially dissolved, and may be present in the form of a suspension or in a separated layer.

[0042] When hydrogen peroxide is used as the stripping-accelerating catalyst, examples of the addition method include adding liquid hydrogen peroxide directly to sulfonic acid or adding a solution containing hydrogen peroxide, such as aqueous hydrogen peroxide, to sulfonic acid. Another example is adding sulfonic acid directly to hydrogen peroxide or aqueous hydrogen peroxide. When nitric acid is used as the stripping-accelerating catalyst, examples of the addition method include adding liquid nitric acid directly to sulfonic acid or adding a solution containing nitric acid, such as aqueous nitric acid, to sulfonic acid and mixing. Another example is adding sulfonic acid directly to nitric acid or aqueous nitric acid.

[0043] The stripping agent, solvent, or treatment liquid may contain one or more types of stripping-promoting catalysts. The inclusion of multiple types of catalysts may stabilize the speed at which the target object is stripped from the substrate.

[0044] (Water) The water contained in the stripper, solvent, and treatment solution of this embodiment may be contained in the stripper, solvent, or treatment solution as water contained in other components used as raw materials, or may be contained in the stripper, solvent, or treatment solution by adding only water. When water is added by adding only water, water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filtration, various adsorption treatments, etc. is particularly preferred, and pure water or ultrapure water is particularly preferred. Such water can be obtained by known methods widely used in semiconductor manufacturing, etc.

[0045] The concentration range of water in the stripping agent, solvent, or treatment solution may be any concentration range that allows for the partial or complete stripping and removal of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the type of stripping-promoting catalyst or sulfonic acid used, the treatment temperature, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of water in the stripping agent, solvent, and treatment solution is preferably 0.01% by weight or more and 70% by weight or less, more preferably 0.1% by weight or more and 70% by weight or less, and even more preferably 0.3% by weight or more and 60% by weight or less, and from the viewpoints of economy and handling safety, 0.6% by weight or more and 60% by weight or less is most preferred.

[0046] When methanesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of water in the stripper, solvent, and treatment solution may be any concentration range that can strip and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the treatment temperature, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of water in the stripper, solvent, and treatment solution is preferably 0.01 wt % or more and 70.0 wt % or less, more preferably 0.3 wt % or more and 40.0 wt % or less, and even more preferably 0.6 wt % or more and 30.0 wt % or less, and from the viewpoints of economy and handling safety, 0.6 wt % or more and 10.0 wt % or less is most preferred.

[0047] When p-toluenesulfonic acid is used as the sulfonic acid and nitric acid is used as the stripping-promoting catalyst, the concentration range of water in the stripper, solvent, and treatment solution may be any concentration range that can strip and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the treatment temperature, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of water in the stripper, solvent, and treatment solution is preferably 1.0 wt % to 70.0 wt %, more preferably 10.0 wt % to 60.0 wt %, and even more preferably 15.0 wt % to 40.0 wt %, and from the viewpoints of economy and handling safety, 20.0 wt % to 30.0 wt % is most preferred.

[0048] When methanesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the stripping-promoting catalyst, the concentration range of water in the stripper, solvent, and treatment solution may be any concentration range that can strip and remove part or all of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the treatment temperature, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of water in the stripper, solvent, and treatment solution is preferably 0.01 wt % to 70.0 wt %, more preferably 0.5 wt % to 40.0 wt %, and even more preferably 1.0 wt % to 35.0 wt %, and from the viewpoints of economy and handling safety, 3.0 wt % to 30.0 wt % is most preferred.

[0049] When p-toluenesulfonic acid is used as the sulfonic acid and hydrogen peroxide is used as the stripping-promoting catalyst, the concentration range of water in the stripping agent, solvent, and treatment solution may be any concentration range that allows for the partial or complete stripping and removal of the resin having an ether bond used from the substrate, and can be appropriately adjusted taking into consideration the treatment temperature, the type, amount, and location of the resin contained in the semiconductor element, the type of functional group, stripping efficiency, handling safety, etc. From the viewpoint of the removal efficiency of the resin having an ether bond, the concentration of water in the stripping agent, solvent, and treatment solution is preferably 0.1 wt % to 70.0 wt %, more preferably 0.5 wt % to 70.0 wt %, and even more preferably 5.0 wt % to 60.0 wt %, and from the viewpoints of economy and handling safety, 10.0 wt % to 30.0 wt % is most preferred.

[0050] When the pH of the stripping agent, solvent, or treatment liquid can be measured, the pH is not particularly limited. However, in order to improve the efficiency of stripping and removing the resin having an ether bond, a lower pH is preferable from the viewpoint of allowing the sulfonic acid to function as an acid.

[0051] (Activator) An activator that activates the peel-promoting catalyst may be added to the stripping agent, solvent, or treatment liquid. By adding the activator, the peel-promoting catalyst is activated, and the speed at which the object is peeled from the substrate may be increased. Furthermore, the reaction between the peel-promoting catalyst and the activator may generate new chemical species in the system, which may increase the speed at which the object is peeled from the substrate.

[0052] For example, when hydrogen peroxide is used as the peel-accelerating catalyst, an activator such as an acid or a radical generator can be used. Examples of such acids include sulfuric acid, nitric acid, nitrous acid, orthophosphoric acid, pyrophosphoric acid, superphosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, vanadic acid, tungstic acid, molybdic acid, chromic acid, osmium tetroxide, and selenium dioxide. Examples of radical generators include urea and amines.

[0053] The inclusion of these activators may cause the stripping agent, solvent, or treatment liquid to generate peracids, radicals, peroxides, or active oxygen, which may increase the speed at which the object is stripped from the substrate.

[0054] On the other hand, an example of an activator for hydrogen peroxide is Fenton's reagent. However, if this Fenton's reagent remains on a semiconductor wafer, as described below, it can cause a decrease in the yield of semiconductor elements. Examples of such Fenton's reagents include iron ions, copper ions, and silver ions. For example, when nitric acid is used as a stripping-promoting catalyst, an activator such as an acid or hydrogen peroxide can be used. Examples of such acids include sulfuric acid, hydrobromic acid, acetic anhydride, and trifluoroacetic acid. The inclusion of these activators can generate peracids, radicals, or nitrogen oxides in the stripping agent, solvent, or treatment solution, which can accelerate the rate at which the target material is stripped from the substrate.

[0055] If desired, other additives conventionally used in semiconductor processing solutions may be added to the stripper, solvent, or processing solution, provided that the purpose of the present invention is not impaired. For example, other additives may include metal corrosion inhibitors, organic solvents, catalysts, complexing agents, chelating agents, surfactants, antifoaming agents, pH adjusters, stabilizers, solubilizers, and precipitation inhibitors. These additives may be added alone or in combination.

[0056] (Stabilizer) A stabilizer may be added to the stripping agent, solvent, or treatment liquid in order to suppress decomposition of the stripping-accelerating catalyst. For example, examples of stabilizers when hydrogen peroxide is used as the stripping-accelerating catalyst include uric acid, barbituric acid, hippuric acid, cyanuric acid, amide compounds such as acetanilide, alkali metal carbonates, and alkali metal hydrogen carbonates.

[0057] Due to the sulfonic acid, or for reasons of convenience in manufacturing the stripper, solvent, or treatment solution, the stripper, solvent, or treatment solution may contain sulfuric acid or a sulfonic acid analogue. Examples of such sulfonic acid analogues include sulfonic acid esters, sulfonamides, sulfinic acids, sulfenic acids, and sulfones. Examples of sulfonic acid esters include methyl methanesulfonate, ethyl methanesulfonate, isopropyl methanesulfonate, phenyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, 2-methoxyethyl p-toluenesulfonate, and ethyl benzenesulfonate. Examples of sulfonamides include methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, p-phenolsulfonamide, and m-nitrobenzenesulfonamide. Examples of sulfinic acids include sulfinic acid, benzenesulfinic acid, and p-toluenesulfinic acid. Examples of sulfenic acids include benzenesulfenic acid. Examples of sulfones include dimethyl sulfone and diethyl sulfone. When these sulfuric acid and sulfonic acid analogues are contained in the stripping agent, solvent, or treatment liquid, they may react with the stripping-promoting catalyst. Therefore, the content of one or more components selected from the group consisting of sulfuric acid and sulfonic acid analogues in the stripping agent, solvent, or treatment liquid is preferably 5 wt% or less, more preferably 2 wt% or less, even more preferably 1 wt% or less, and most preferably 0.5 wt% or less.

[0058] The stripping agent, solvent, or treatment liquid may contain alkali metal ions, alkaline earth metal ions, etc., derived from the stripping-promoting catalyst or additive, or for reasons of manufacturing the stripping agent, solvent, or treatment liquid. However, if these alkali metal ions and alkaline earth metal ions remain on the semiconductor wafer, they are likely to cause a decrease in the yield of semiconductor elements, etc.

[0059] Furthermore, the presence of metal ions such as chromium, manganese, iron, cobalt, copper, molybdenum, or tungsten in the stripping agent, solvent, or treatment liquid may cause decomposition of the stripping-promoting catalyst, etc. Therefore, the content of the metal in the stripping agent, solvent, or treatment liquid, specifically, for example, any metal selected from lithium, sodium, potassium, aluminum, magnesium, calcium, chromium, manganese, iron, nickel, cobalt, copper, silver, cadmium, barium, tin, zinc, molybdenum, tungsten, and lead, is preferably 1 ppb or less, more preferably 0.5 ppb or less, even more preferably 0.2 ppb or less, and most preferably 0.1 ppb or less, and may also be 0.01 ppt or more, on a weight basis. Furthermore, among the above metals, the concentration of any one metal selected from iron, copper, manganese, chromium, and zinc is preferably 0.01 ppt to 1 ppb by weight, more preferably 0.01 ppt to 0.5 ppb, even more preferably 0.01 ppt to 0.2 ppb, and most preferably 0.01 ppt to 0.1 ppb. Furthermore, in the above explanation, ionic metals have been mentioned as metals that may be contained in the stripper, solvent, or treatment solution, but this is not limiting, and non-ionic metals (particulate metals) may also be contained, and the concentration thereof is preferably within the above range.

[0060] The stripping agent, solvent, or treatment liquid may contain gases such as hydrogen or oxygen due to the stripping-promoting catalyst or additive, or for reasons of manufacturing the stripping agent, solvent, or treatment liquid.

[0061] The stripping agent, solvent, or treatment liquid may contain active oxygen species, peracids such as persulfonic acid, or nitrogen oxides derived from sulfonic acid, stripping-promoting catalyst, or activator, or for reasons of manufacturing the stripping agent, solvent, or treatment liquid. Examples of such active oxygen species include perhydroxy anion (O ２ H － ), or peroxide anion (.O ２ ２－ ), hydroxonium cation (OH ＋), perhydroxyl radical (.HO ２ ), hydroxyl radical (·OH), or superoxide anion radical (·O ２ － ) or singlet oxygen. Examples of such nitrogen oxides include nitrosonium ions (NO ＋ ), nitronium ion (NO ２ ＋ ), nitrate ions (NO ３ － ), nitrite ion (NO ２ － ), hyponitrite ion (NO － ), nitrogen dioxide (NO ２ ), nitrogen trioxide (N ２ O ３ ), dinitrogen tetroxide (N ２ O ４ ), or dinitrogen pentoxide (N ２ O ５ ) etc.

[0062] The inventors speculate that the reason why strippers, solvents, or treatment solutions are effective against resins having ether bonds is that the action of an oxidizing agent such as hydrogen peroxide with sulfonic acid generates active oxygen species or persulfonic acid, and because sulfonic acid is a strong acid, it reacts with acids such as nitric acid to generate active species such as nitrogen oxides, which are involved in the cleavage of the ether bond. These active oxygen species, persulfonic acid, or nitrogen oxides act on the ether bond of the resin having an ether bond, cleaving the ether bond, and the oxygen atom derived from the cleaved ether bonds and the sulfonic acid group derived from the sulfonic acid bond. This is thought to decompose the three-dimensional structure of the resin having an ether bond, causing it to dissolve and become miscible in the sulfonic acid. Furthermore, because sulfonic acid is an organic acid, it is hydrophobic, improving the contact angle and penetrating and swelling the resin, which is thought to be why it is more effective than other inorganic acids.

[0063] There are no particular limitations on the method for producing the stripping agent, solvent, or treatment liquid described above, and they can be prepared by blending the above-described components in desired amounts.

[0064] (Removal Method) Another embodiment of the present invention is a method for removing a resin having an ether bond from a semiconductor substrate, which comprises contacting the resin having an ether bond with the above-described remover at a temperature of 20° C. or higher and 200° C. or lower. The conditions for the above-described treatment can be applied to the removal conditions such as time, temperature, and atmosphere, and the conditions described below in the method for manufacturing a semiconductor element can also be applied as desired.

[0065] (Method for Manufacturing Semiconductor Devices) The above-described stripping agent, solvent, or treatment liquid can be suitably used in a resin processing step, a resin stripping step, a resin removal step, a residue removal step, a cleaning step, or the like in semiconductor manufacturing. Furthermore, the above-described stripping agent, solvent, or treatment liquid can be used directly in a method for manufacturing a semiconductor device. For example, a method for manufacturing a semiconductor device can be adopted that includes a step of performing stripping by the above-described stripping method. The method for manufacturing a semiconductor device may include known steps used in semiconductor device manufacturing, such as one or more steps selected from a wafer fabrication step, an oxide film formation step, a transistor formation step, a wiring formation step, and a CMP step. In a method for manufacturing a semiconductor device according to an embodiment described below, a stripping agent, solvent, or treatment liquid is used in a stripping step in which a resin having an ether bond is stripped from a semiconductor substrate. The above-described processing step, resin removal step, residue removal step, cleaning step, or the like can be treated as one aspect of the stripping step.

[0066] (Reuse of Processing Liquid) After semiconductor devices are manufactured using a stripper, solvent, or processing liquid, the used liquid may be reused. Here, the used liquid refers to a stripper, solvent, or processing liquid that has been used at least once in a process such as a resin removal step during the manufacture of semiconductor wafers. Furthermore, when reusing the used liquid, the used liquid may be recycled, a new stripping-promoting catalyst may be added to the used liquid, the sulfonic acid in the used liquid may be concentrated to reduce the water content, or the solid sulfonic acid in the used liquid may be collected by filtration and then reused.

[0067] (Object to be treated, substrate) The object to be treated with the stripping agent, solvent, or treatment solution is a resin having an ether bond attached to a substrate. The resin having an ether bond may be attached to the substrate via a chemical bond or a physical bond, or may be attached via an adhesive layer or the like. In addition, a part or all of the resin having an ether bond is the object to be treated. The material of the substrate is not particularly limited, and examples thereof include Si (silicon), Si compounds, ceramic, arsenic, phosphorus, metals, or metal compounds, and as a semiconductor substrate, Si or Si compounds are particularly preferred.

[0068] The Si compound is not particularly limited, and examples thereof include silicon oxide, silicon dioxide, glass silica, quartz, quartz, silicon carbide, silicon nitride, mica, clay, and calcium silicate. The metal is not particularly limited, and examples thereof include aluminum, gallium, chromium, cobalt, nickel, zinc, platinum, germanium, tantalum, and samarium. The metal compound is not particularly limited, and examples thereof include alumina, zirconia, ferrite, titania, magnesia, and aluminum hydroxide.

[0069] (Resin Having an Ether Bond) The resin having an ether bond is not particularly limited, but examples thereof include polyoxymethylene, polyphenylene ether, polyurethane resin, cyanate resin, phenol resin, cresol resin, xylenol resin, p-t-butylphenol resin, p-phenylphenol resin, resorcinol resin, epoxy resin, polyetherimide, polyethersulfone, polythioethersulfone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyaryletherketone, polyethernitrile, and ethyl cellulose. From the viewpoints of chemical resistance, moisture resistance, heat resistance, and suitability for use in semiconductor applications, polyurethane resin, phenol resin, cresol resin, epoxy resin, polyetherimide, and polyethersulfone are preferred, and from the viewpoints of chemical resistance, moisture resistance, heat resistance, and the like, epoxy resin or polyetherimide is most preferred.

[0070] Hereinafter, a specific description will be given of an example in which an epoxy resin is used as the resin having an ether bond.

[0071] (Epoxy Resin) Epoxy resins can be obtained by reacting a pre-cured epoxy resin with its curing agent, and other additives such as crosslinkers, curing accelerators, catalysts, elastomers, or flame retardants may also be added. The pre-cured epoxy resin is not particularly limited, but examples thereof include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AD ​​epoxy resins, brominated bisphenol A epoxy resins, novolac glycidyl ethers, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polybasic acids, and cresol novolac epoxy resins. Epoxy resins are excellent in terms of, for example, electrical properties, adhesiveness, and chemical resistance.

[0072] (Curing Agent) The curing agent is not particularly limited, and examples thereof include acid anhydrides, amine compounds, phenolic compounds, isocyanate compounds, organic phosphorus compounds, latent curing agents, cationic polymerization curing agents, anionic polymerization curing agents, and organic metal derivatives. Examples of acid anhydrides include phthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, and nadic anhydride.

[0073] Examples of the amine compound include hexamethylenetetraamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenylsulfone, and metaphenylenediamine. Examples of the phenol compound include hydroquinone, resorcinol, catechol, bisphenol A novolac, bisphenol F novolac, naphthalenediol, phenol aralkyl, biphenol novolac, phenol novolac, and halides, alkyl group-substituted compounds, and polycondensates thereof. Examples of the isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane isocyanate, xylylene diisocyanate, and tolylene diisocyanate.

[0074] Examples of organic phosphorus compounds include hexamethylphosphoric triamide and triphenylphosphine. Examples of latent curing agents include dicyandiamide and ketimine. Examples of cationic polymerization curing agents include boron trifluoride-amine complexes. Examples of anionic polymerization curing agents include 2-ethyl-4-methylimidazole. Examples of metal organic derivatives include zinc naphthenate and zinc stearate. These curing agents may be used alone or in combination of two or more.

[0075] Examples of the curing accelerator include an imidazole compound, a tertiary amine compound, a quaternary ammonium salt, an organic phosphorus compound, etc. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0076] (Additives) The epoxy resin may contain various additives for the purpose of improving the resin properties of the epoxy resin. Examples of additives that can be used include inorganic fillers, emulsifiers, foaming agents, stabilizers, plasticizers, lubricants, flame retardant assistants, antistatic agents, colorants, chargeability imparting agents, and reactive diluents.

[0077] The inorganic filler is not particularly limited, and examples thereof include carbonates, sulfates, silicon compounds, titanate compounds, boron compounds, hydroxides, oxides, nitrides, and carbon-based fillers. Examples of carbonates include calcium carbonate and magnesium carbonate. Examples of sulfates include barium sulfate and calcium sulfate. Examples of silicon compounds include talc, mica, kaolin clay, wollastonite, sepiolite, hydrotalcite, montmorillonite, glass, silica, clay, and mica. Examples of titanate compounds include potassium titanate. Examples of boron compounds include aluminum borate. Examples of hydroxides include aluminum hydroxide, magnesium hydroxide, and calcium hydroxide. Examples of oxides include titanium oxide, zinc oxide, aluminum oxide, and magnesium oxide. Examples of nitrides include boron nitride and aluminum nitride. Examples of carbon-based fillers include carbon black, graphite, and carbon fiber.

[0078] The size of the resin having an ether bond to be treated is not particularly limited, and may be any size that can be treated in accordance with the scale of the treatment equipment and semiconductor element.

[0079] (Step of Peeling Off Resin Having an Ether Bond) A method for manufacturing a semiconductor element according to another embodiment of the present invention includes a step of performing a treatment (peeling treatment) to peel off a resin having an ether bond from a substrate (hereinafter referred to as the peeling step). This treatment refers to partially or completely peeling off a resin having an ether bond from a substrate using the above-mentioned peeling agent, solvent, or treatment liquid. These peeling steps include, for example, peeling off an adhesive layer between a substrate and a resin, or partially peeling off a resin from a resin layer. Furthermore, the substrate may be a semiconductor substrate.

[0080] (Speed ​​at which the object is peeled from the substrate) The speed at which the object is peeled from the substrate (hereinafter referred to as peeling speed) refers to the speed at which the above-mentioned peeling step is carried out and the resin having an ether bond attached to the substrate is partially or completely peeled from the substrate. From the viewpoint of the efficiency of removing the resin having an ether bond, a faster peeling speed is preferable. The peeling speed varies depending on the type of resin, chemical resistance, amount present, location present, type of functional group, resin characteristics, etc., but specifically, it is preferably 3.0 μm / min or more, and more preferably 3.5 μm / min or more. Furthermore, a peeling speed of 0.2 μm / min or less is not practical.

[0081] (Treatment step for swelling the resin having an ether bond) In the peeling step, a treatment step (hereinafter referred to as a swelling treatment) can be incorporated as a pretreatment or intermediate treatment for the peeling process, in which the resin having an ether bond is immersed in a heated organic solvent to cause a volume change in the resin having an ether bond. By providing such a swelling treatment, it is possible to reduce the adhesive force between the resin having an ether bond and the substrate, thereby increasing the efficiency of peeling the resin having an ether bond from the substrate, reducing the time required for production, and enabling peeling from the substrate even under milder conditions.

[0082] As the organic solvent used in the swelling treatment, a polar solvent such as water may be contained in the release agent used in the peeling treatment after the swelling treatment, so it is preferable to use a polar solvent. These polar solvents may contain water, and the solvent may be one type or multiple types. Examples of the solvent include polar solvents such as alcohols, ketones, nitriles, ethers, esters, carboxylic acids, sulfur-containing compounds, and nitrogen-containing compounds.

[0083] Examples of polar alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 3-heptanol, dodecanol, cyclohexanol, 1-methylcyclohexanol, phenol, m-cresol, benzyl alcohol, phenoxyethanol, salicylic alcohol, anisyl alcohol, anise alcohol, phenethyl alcohol, 2-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methylbenzyl alcohol, 4-methylbenzyl alcohol, 2-ethoxybenzoic acid ... Examples of polar solvents include ethylbenzyl alcohol, 4-ethylbenzyl alcohol, 2-methoxyphenethyl alcohol, 4-methoxybenzyl alcohol, 4-ethoxybenzyl alcohol, vanillyl alcohol, veratryl alcohol, cinnamyl alcohol, benzhydrol, trityl alcohol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, and glycerin. Examples of polar solvents for ketones include acetone. Examples of polar solvents for nitriles include acetonitrile and propanenitrile.

[0084] Examples of polar solvents for ethers include tetrahydrofuran, etc. Examples of polar solvents for esters include methyl acetate, ethyl acetate, or propylene carbonate, etc. Examples of polar solvents for carboxylic acids include formic acid or acetic acid, etc. Examples of polar solvents for sulfur-containing compounds include dimethyl sulfoxide, dimethyl sulfone, or sulfolane, etc.

[0085] Examples of polar solvents for nitrogen-containing compounds include N,N,N',N'-tetramethylurea, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformamide, N-methylacetamide, N-methyl-2-pyrrolidone, acetamide, nitromethane, etc. Among these solvents, 1-pentanol, 1-hexanol, phenol, cresol, benzyl alcohol, salicyl alcohol, anisyl alcohol, anise alcohol, phenethyl alcohol, vanillyl alcohol, veratryl alcohol, cinnamyl alcohol, benzhydrol, trityl alcohol, ethylene glycol, propylene glycol, diethylene glycol, butanediol, glycerin, dimethyl sulfoxide, dimethyl sulfone, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferred because they have high boiling points and allow the swelling step to be carried out at high temperatures.

[0086] Furthermore, from the viewpoint of easy availability of low-cost, high-purity products, phenol, cresol, benzyl alcohol, anise alcohol, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone are more preferred. Furthermore, from the viewpoint of easy availability of high-purity products for semiconductors, benzyl alcohol, ethylene glycol, glycerin, dimethyl sulfoxide, and N-methyl-2-pyrrolidone are even more preferred. Furthermore, dimethyl sulfoxide is most preferred because it promotes peeling of resins having ether bonds from substrates.

[0087] When a swelling treatment is included, the temperature of the swelling treatment may be any temperature that can reduce the adhesive strength between the resin having an ether bond and the substrate, and can be appropriately adjusted taking into consideration the type, chemical resistance, amount present, location present, and type of functional group of the resin contained in the semiconductor element, as well as resin properties such as the resin's glass transition temperature, and the type of organic solvent. From the viewpoint of the efficiency of removing the resin having an ether bond, this temperature is preferably 20°C or higher and 400°C or lower, more preferably 20°C or higher and 300°C or lower, and even more preferably 50°C or higher and 250°C or lower, and most preferably 50°C or higher and 200°C or lower from the viewpoint of handling safety. If the temperature is within the above range, the adhesive strength between the resin having an ether bond and the substrate can be reduced, and the resin having an ether bond can be efficiently removed in the subsequent peeling step.

[0088] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0089] (Substrate containing resin having ether bond) An epoxy resin composition was prepared using a bisphenol A type epoxy resin ("jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation) as the resin having an ether bond, a phenol compound ("jER Cure (registered trademark) 170" manufactured by Mitsubishi Chemical Corporation) as the curing agent, and imidazole as the curing accelerator. The compounding ratio of the epoxy resin to the curing agent was adjusted so that the epoxy equivalent / hydroxyl group equivalent was 1. Next, a silicon wafer was impregnated with the obtained epoxy resin composition and cured in a dryer at 150°C for 30 minutes to obtain a substrate containing the epoxy resin with a resin thickness of approximately 0.5 to 1.0 mm. The obtained substrates were each cut into 10 mm x 20 mm to prepare test pieces. Using this epoxy resin as a standard, it was confirmed that a predetermined peeling rate could be obtained using the release agent and conditions shown in Example 1, and other Examples and Comparative Examples were investigated.

[0090] (Evaluation of peeling rate by release agent) The test piece obtained as described above was immersed in a release agent for a predetermined time, and the peeling rate before and after was evaluated by the following method. The epoxy resin on the Si substrate was observed using a digital microscope (Keyence Corporation, VHX-8000), and the difference in thickness of the epoxy resin before and after immersion in the release agent was calculated to evaluate the amount of peeling. This amount of peeling was divided by the treatment time to evaluate the peeling rate [μm / min].

[0091] (Evaluation of the amount of dissolution in solvent) The test piece obtained as described above was immersed in a solvent for a predetermined time, and the amount of resin dissolved before and after was evaluated by the following method. Using a laser microscope (Keyence Corporation, VK-9710), the volume of the epoxy resin on the Si substrate was measured, and the volume reduction rate before and after immersion in the solvent was calculated and evaluated according to the following criteria: A: Completely dissolved (reduction rate: 100%) B: Reduction rate: 50% or more but less than 100% C: Reduction rate: 10% or more but less than 50% D: Reduction rate: less than 10%

[0092] (Evaluation of Smoothness of Si Substrate by Treatment Solution) The test pieces obtained as described above were immersed in the treatment solution for a predetermined time, and the smoothness of the Si substrate was evaluated as follows. Using a field emission scanning electron microscope (JSM-7800F Prime, manufactured by JEOL Ltd.), the Si substrate surface was observed to confirm the presence or absence of surface roughness, and evaluated according to the following criteria: A: No surface roughness was observed. B: Surface roughness was observed. C: Surface roughness was observed, and a change in the surface area of ​​the Si substrate was observed compared to before immersion. Note that a small change in the Si substrate indicates little corrosion of the Si.

[0093] (Preparation of Remover, Semiconductor Element Manufacturing Method) <Examples 1 to 12> A rotor (manufactured by AsOne, total length 30 mm x diameter 8 mm) was placed in a three-neck flask, a thermometer protection tube (manufactured by Cosmos Bead, bottom-sealed type) and a thermometer were placed in one opening, a PFA tube (manufactured by Flon Industries Co., Ltd., F-8011-02) connected to a nitrogen gas cylinder was connected to the other opening, and a Dimroth condenser (manufactured by AsOne, model number 4-421-04) was connected to the remaining opening. Methanesulfonic acid (manufactured by Fujifilm Wako Corporation, MSA) was added to the three-neck flask. Thereafter, hydrogen peroxide solution (30 wt%, manufactured by Fujifilm Wako Corporation) was added so as to obtain the composition shown in Table 1, thereby obtaining a resin remover having an ether bond (semiconductor remover). After the prepared release agent was heated to the temperature listed in Table 1, the test piece was placed in a three-neck flask and immersed for the time listed in Table 1. In Examples 1 to 5 and 9 to 12, the container was allowed to cool naturally to 100°C before the test piece was removed. In Examples 6 to 8, the test piece was removed without cooling the container. The release rate of the resin was evaluated using the method described in the above section (Evaluation of Release Rate by Release Agent), and the results are shown in Table 1. In each experimental example, when water was contained in each raw material, it served as a solvent. When no other solvent was used, water was the only solvent. The type of solvent and its concentration in the release agent are listed in the following tables. When a component other than water was used as a solvent, this component was treated as the solvent, and its type and concentration are listed in each table.

[0094] Examples 13 to 25 In Examples 13 to 25, treatment with a stripping agent (semiconductor stripping agent) was carried out under the conditions set forth in Table 1 in the same manner as in Examples 1 to 5, except that a stripping-promoting catalyst having the composition set forth in Table 1 was used. The stripping rates of the resins were evaluated using the method described above in the section (Evaluation of Stripping Rates by Stripping Agents), and the results are shown in Table 1. In Examples 21 to 23, the test specimens were immersed and then removed without cooling the container. In Example 13, orthoperiodic acid (98.5 wt % orthoperiodic acid, manufactured by Fujifilm Wako Co., Ltd.) was used as the stripping-promoting catalyst; in Example 14, hydrogen bromide (47 wt % hydrobromic acid, manufactured by Fujifilm Wako Co., Ltd.) was used as the stripping-promoting catalyst; and in Examples 15 to 25, nitric acid (70 wt % aqueous nitric acid solution, manufactured by Fujifilm Wako Co., Ltd.) was used as the stripping-promoting catalyst. The orthoperiodic acid used in Example 13 has the molecular formula HIO ４ ・2H ２ Since the water in Table 1 is periodic acid dihydrate represented by 1,0, the water in Table 1 includes water derived from the hydrate. This also applies to the orthoperiodic acid hydrates in Examples 51 and 81 described below, and the water in Tables 4 and 7 also includes water derived from the hydrate.

[0095] Example 26 In Example 26, similar to Examples 1 to 25, a thermometer protection tube (Cosmos Bead, bottom-sealed type) and a thermometer were placed in one opening, a PFA tube (Flon Industries, F-8011-02) connected to a nitrogen gas cylinder was connected to the other opening, and the remaining opening was connected to a Dimroth condenser (AsOne, model number 4-421-04). Nitric acid (60 wt % nitric acid aqueous solution, Fujifilm Wako Co., Ltd.) was added as a stripping-promoting catalyst to the three-neck flask to obtain the composition shown in Table 1. Methanesulfonic acid (Fujifilm Wako Co., Ltd.) was then added to obtain the composition shown in Table 1, thereby obtaining a resin stripping agent (semiconductor stripping agent) having an ether bond. The prepared stripping agent was heated to the temperature shown in Table 1, and the test piece was placed in the three-neck flask and immersed for 30 minutes, after which the test piece was removed. The peeling speed of the resin was evaluated by the method described above in the section (Evaluation of peeling speed by release agent), and the results are shown in Table 1.

[0096]

[0097] Examples 27 to 41 In Examples 27 to 41, similar to Examples 1 to 26, a thermometer protection tube (Cosmos Bead, bottom-sealed type) and a thermometer were placed in one opening, a PFA tube (Flon Industries, F-8011-02) connected to a nitrogen gas cylinder was connected to the other opening, and a Dimroth condenser (AsOne, model number 4-421-04) was connected to the remaining opening. A stripping-promoting catalyst as listed in Table 1 was added to the three-neck flask. Then, p-toluenesulfonic acid (Fujifilm Wako, TSA) was added to obtain the composition listed in Table 2, thereby obtaining a resin stripping agent (semiconductor stripping agent) having an ether bond. The prepared stripping agent was heated to the temperature listed in Table 2, and the test piece was then placed in the three-neck flask and immersed for the time listed in Table 2, after which the test piece was removed. The release rates of the resins were evaluated by the method described above in the section (Evaluation of release rate by release agent), and the results are shown in Table 2. Note that in Examples 27 to 32, hydrogen peroxide (30 wt % hydrogen peroxide solution, manufactured by Fuji Film Wako Co., Ltd.) was used as the release-accelerating catalyst, in Example 33, hydrogen bromide (47 wt % hydrobromic acid, manufactured by Fuji Film Wako Co., Ltd.) was used as the release-accelerating catalyst, and in Examples 34 to 41, nitric acid (70 wt % nitric acid aqueous solution, manufactured by Fuji Film Wako Co., Ltd.) was used as the release-accelerating catalyst.

[0098]

[0099] Comparative Examples 1 to 11 In Comparative Examples 1 to 11, treatment with a stripping agent (semiconductor stripping agent) was carried out under the conditions shown in Table 3 in the same manner as in Examples 1 to 26, except that the compositions shown in Table 3 were used. The stripping rates of the resins were evaluated by the method described above in the section (Evaluation of Stripping Rates by Stripping Agents), and the results are shown in Table 3. In Comparative Example 2, 37 wt % hydrochloric acid (manufactured by Fujifilm Wako Co., Ltd.) was used as HCl, in Comparative Example 3, 48 wt % aqueous sodium hydroxide solution (manufactured by Hayashi Pure Chemical Industries Co., Ltd.) was used as NaOH, and in Comparative Example 4, 37 wt % aqueous sodium hydroxide solution (manufactured by Hayashi Pure Chemical Industries Co., Ltd.) was used as NaOH. ２ O ２In Comparative Example 5, 30 wt% hydrogen peroxide solution (manufactured by Fuji Film Wako Corporation) was used, in Comparative Example 6, 30 wt% hydrogen peroxide solution (manufactured by Fuji Film Wako Corporation) and 98 wt% sulfuric acid (manufactured by Fuji Film Wako Corporation) were used, in Comparative Example 7, benzyl alcohol (manufactured by Fuji Film Wako Corporation) and potassium phosphate (manufactured by Fuji Film Wako Corporation) were used, in Comparative Example 8, potassium hydroxide (manufactured by Fuji Film Wako Corporation) and N-methylpyrrolidone (manufactured by Fuji Film Wako Corporation) were used, in Comparative Example 9, methanesulfonic acid (manufactured by Fuji Film Wako Corporation) was used, in Comparative Example 10, p-toluenesulfonic acid (manufactured by Fuji Film Wako Corporation) was used, and in Comparative Example 11, HNO ３ As the solvent, a 70 wt % aqueous solution of nitric acid (manufactured by Fujifilm Wako Co., Ltd.) was used.

[0100]

[0101] <Examples 42 to 58> In the same manner as in Examples 1 to 26, treatment with a solvent (semiconductor solvent) was carried out under the conditions shown in Table 4, and the amount of resin dissolved was evaluated by the method described above in the section (Evaluation of amount dissolved by solvent), and the results are shown in Table 4.

[0102]

[0103] <Examples 59 to 72> In the same manner as in Examples 27 to 41, treatment with a solvent (semiconductor solvent) was carried out under the conditions shown in Table 5, and the amount of resin dissolved was evaluated by the method described above in the section (Evaluation of amount dissolved by solvent), and the results are shown in Table 5.

[0104]

[0105] Comparative Examples 12 to 14 In Comparative Examples 12 to 14, treatment with a solvent (semiconductor solvent) was carried out under the conditions shown in Table 6 in the same manner as in Examples 1 to 26, except that the compositions shown in Table 6 were used. The amount of resin dissolved was evaluated by the method described above in the section (Evaluation of amount dissolved by solvent), and the results are shown in Table 6. In Comparative Example 12, benzyl alcohol (manufactured by FUJIFILM Wako Corporation) and potassium phosphate (manufactured by FUJIFILM Wako Corporation) were used, in Comparative Example 13, potassium hydroxide (manufactured by FUJIFILM Wako Corporation) and N-methylpyrrolidone (manufactured by FUJIFILM Wako Corporation) were used, and in Comparative Example 14, phosphoric acid (manufactured by FUJIFILM Wako Corporation) and N-methylpyrrolidone (manufactured by FUJIFILM Wako Corporation) were used.

[0106]

[0107] Examples 73 to 88 In the same manner as in Examples 1 to 26, treatments were carried out using treatment solutions (semiconductor treatment solutions) under the conditions shown in Table 7, and the smoothness of the Si substrates was evaluated by the method described above in the section (Evaluation of smoothness of Si substrates using treatment solutions), and the results are shown in Table 7.

[0108]

[0109] Examples 89 to 102 In the same manner as in Examples 27 to 41, treatments were carried out using treatment solutions (semiconductor treatment solutions) under the conditions shown in Table 8, and the smoothness of the Si substrates was evaluated by the method described above in the section (Evaluation of smoothness of Si substrates using treatment solutions), and the results are shown in Table 8.

[0110]

[0111] Comparative Examples 15 to 17 In Comparative Examples 15 to 17, treatment with a treatment liquid (semiconductor treatment liquid) was carried out under the conditions shown in Table 9 in the same manner as in Examples 1 to 26, except that the compositions shown in Table 9 were used. The smoothness of the Si substrates was evaluated by the method described above in the section (Evaluation of Smoothness of Si Substrates Using Treatment Liquid), and the results are shown in Table 9. In Comparative Example 15, a 48 wt % aqueous solution of sodium hydroxide (manufactured by Hayashi Pure Chemical Industries, Ltd.) was used as NaOH; in Comparative Example 16, benzyl alcohol (manufactured by FUJIFILM Wako Corporation) and potassium phosphate (manufactured by FUJIFILM Wako Corporation) were used; and in Comparative Example 17, potassium hydroxide (manufactured by FUJIFILM Wako Corporation) and N-methylpyrrolidone (manufactured by FUJIFILM Wako Corporation) were used.

[0112]

Claims

1. A release agent used to remove a resin having an ether bond from a substrate, comprising a sulfonic acid, a release-promoting catalyst, and water.

2. The stripping agent according to claim 1, wherein the stripping-promoting catalyst is at least one selected from the group consisting of oxidizing agents and acid catalysts.

3. The stripping agent according to claim 2, wherein the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, halogen oxygen acid, hydrohalic acid, halogen, and ozone.

4. The stripping agent according to claim 3, wherein the halogen oxygen acid is at least one selected from the group consisting of orthoperiodic acid and orthoperiodate ions.

5. The stripping agent according to claim 2, wherein the acid catalyst is at least one selected from the group consisting of hydrogen halides, sulfuric acid, nitric acid, and nitrite.

6. The release agent according to claim 1, wherein the resin having the ether bond is an epoxy resin.

7. A stripping agent for semiconductors, according to any one of claims 1 to 6.

8. A method for peeling off a resin having ether bonds from a semiconductor substrate, A method for peeling off a resin having an ether bond, comprising contacting the peeling agent described in claim 7 with the resin at a temperature of 20°C to 200°C.

9. A method for manufacturing a semiconductor device, comprising the step of performing peeling by the peeling method described in claim 8.

10. A semiconductor solvent used to dissolve a resin having an ether bond and to peel it off from a semiconductor substrate, comprising a sulfonic acid, a peel-promoting catalyst, and water.

11. A semiconductor processing solution used to remove resins containing ether bonds from semiconductor substrates. A semiconductor processing solution characterized by containing sulfonic acid, a stripping catalyst, and water.

12. A method for manufacturing a semiconductor device, comprising a peeling step of peeling a resin having ether bonds from a semiconductor substrate using the semiconductor solvent described in claim 10 or the semiconductor processing liquid described in claim 11, wherein the processing is performed at a temperature of 20°C or higher and 200°C or lower.