Cleaner composition for adhesive

Abstract

To provide a cleaner composition for an adhesive, which is superior in the property of removing an adhesive in an embodiment hereof.SOLUTION: A cleaner composition for an adhesive, herein disclosed is arranged for removing an adhesive 2 remaining on a wafer 3 in an embodiment. The cleaner composition comprises an organic solvent, and a surfactant. The surfactant is at least one kind selected from a group consisting of a fluorine-based surfactant and a silicone-based surfactant. The content of the organic solvent is 90 mass% or more and 99.97 mass% or less, and the content of the surfactant is 0.03 mass% or more and 5 mass% or less.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present disclosure relates to a cleaning composition for adhesives, and a method for producing and cleaning a semiconductor substrate using the same. [Background technology]

[0002] In recent years, the high integration of semiconductor devices has progressed dramatically, and three-dimensional integrated circuit (3DIC) technology has attracted attention. 3DIC technology is a technique for stacking wafers in multiple layers while connecting them using through-silicon vias (TSVs) and other methods. When stacking wafers in multiple layers, it is necessary to thin the backside of the wafer on which the circuits are formed (the side on which the circuits are not formed) by polishing, and then form electrodes on the backside. Before thinning, the wafer is bonded (temporarily bonded) to a fixing member (support) with an adhesive, and after undergoing processes such as polishing and electrode formation, the wafer is separated from the fixing member. The adhesive often remains on the wafer after it has been separated from the fixing member, which can cause problems in subsequent processes. Therefore, a cleaning process is carried out to remove any adhesive remaining on the wafer.

[0003] A variety of compositions have been developed to remove such adhesive residues. For example, Patent Document 1 discloses a rework solvent for cleaning an adhesive layer attached to a peeled semiconductor circuit-forming substrate or a support substrate, the rework solvent containing at least an amine-based solvent and a specific glycol ether-based solvent. Furthermore, as a composition for removing residues other than adhesives, Patent Document 2, for example, proposes a treatment liquid for semiconductor devices that contains at least one hydroxyallylamine compound selected from hydroxylamine and hydroxylamine salts, an organic basic compound, an alcohol-based solvent, and a surfactant as a treatment liquid for removing dry etching residues. In an example of this document, for example, a treatment liquid containing 60% by mass of diethylene glycol monobutyl ether as the alcohol-based solvent and 0.1% by mass of cetyltrimethylammonium bromide as the surfactant is disclosed. Patent Document 3 proposes a stripper composition for removing photoresist, which contains a chain amine compound with a weight-average molecular weight of 95 g / mol or more, a chain amine compound with a weight-average molecular weight of 90 g / mol or less, a cyclic amine compound, an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with one or two nitrogen atoms, and a polar organic solvent. The examples in this document disclose a stripper removal composition containing 55.5 mass % of diethylene glycol monomethyl ether and 20.0 mass % of diethylene glycol monomethyl ether as polar organic solvents, and 0.01 mass % of polyether-modified polydimethylsiloxane as a surfactant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2016 / 021646 issue [Patent Document 2] WO2019 / 187868 [Patent Document 3] Special Publication No. 2017-527838 Summary of the Invention [Problem to be solved by the invention]

[0005] In the manufacturing process of three-dimensional integrated circuits (3DIC), processing such as electrode formation after polishing a wafer that has been bonded (temporarily bonded) with an adhesive to a fixing member (support) may be carried out at high temperatures of 150°C or higher, and if the adhesive changes in quality due to heating, it tends to be difficult to remove. Cleaning compositions are required to have excellent removability (cleaning properties) for such adhesives. However, the compositions proposed in Patent Documents 1 to 3 do not have sufficient adhesive removability.

[0006] Therefore, the present disclosure provides an adhesive cleaning composition that has excellent adhesive removal properties, and a method for producing and cleaning a semiconductor substrate using the same. [Means for solving the problem]

[0007] In one aspect, the present disclosure relates to a cleaning composition for adhesives for removing adhesive remaining on a wafer, the cleaning composition comprising an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, the content of component A being 90% by mass or more and 99.97% by mass or less, and the content of component B being 0.03% by mass or more and 5% by mass or less.

[0008] In one aspect, the present disclosure relates to an adhesive remover for removing adhesive remaining on a wafer, the adhesive remover comprising an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, the content of component A being 90% by mass or more and 99.97% by mass or less, and the content of component B being 0.03% by mass or more and 5% by mass or less.

[0009] In one aspect, the present disclosure relates to a method for producing a semiconductor substrate, the method comprising: (1) bonding a wafer to a fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the surface bonded to the fixing member; (3) processing the polished surface of the wafer; (4) separating the processed wafer from the fixing member; and (5) removing any adhesive remaining on the separated wafer with a cleaning agent, wherein the cleaning agent is a cleaning agent composition containing an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, and the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less.

[0010] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate, comprising: (1) bonding a wafer to a fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the surface bonded to the fixing member; (3) processing the polished surface of the wafer; (4) separating the processed wafer from the fixing member; and (5) removing adhesive remaining on the separated wafer with an adhesive remover, wherein the adhesive remover contains an organic solvent (component A) and a surfactant (component B), and component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, and the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less.

[0011] In one aspect, the present disclosure relates to a cleaning method, comprising a step of removing the adhesive remaining on the wafer with a cleaning agent after separating the wafer, which has been bonded to a fixing member with an adhesive, from the fixing member, wherein the cleaning agent is a cleaning agent composition containing an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, and the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less.

[0012] In one aspect, the present disclosure relates to an adhesive removal method, comprising a step of removing adhesive remaining on a wafer with an adhesive remover after separating the wafer, which has been adhesively bonded to a fixing member, from the fixing member, wherein the adhesive remover contains an organic solvent (component A) and a surfactant (component B), component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, the content of component A being 90% by mass or more and 99.97% by mass or less, and the content of component B being 0.03% by mass or more and 5% by mass or less. [Effects of the Invention]

[0013] According to the present disclosure, it is possible to provide an adhesive cleaning composition that is excellent in adhesive removability, and a semiconductor substrate manufacturing method and cleaning method that use the same. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a flowchart showing the steps of a method for manufacturing a semiconductor substrate according to the present disclosure. [Figure 2] FIG. 2 is a schematic diagram illustrating each step in one embodiment of the method for manufacturing a semiconductor substrate according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present disclosure is based on the finding that adhesives can be efficiently removed by using a cleaning composition containing a predetermined amount of an organic solvent and a specific surfactant.

[0016] In one aspect, the present disclosure relates to a cleaning composition for adhesives (hereinafter also referred to as "the cleaning composition of the present disclosure") for removing adhesives remaining on wafers, the cleaning composition comprising an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, and the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less.

[0017] According to the present disclosure, a cleaning composition having excellent adhesive removal properties can be provided. Furthermore, by using the cleaning composition of the present disclosure, high-quality semiconductor substrates can be obtained in high yield.

[0018] Although the details of the mechanism of action by which the effects of the present disclosure are manifested are still unclear, it is presumed as follows. In the cleaning composition of the present disclosure, it is believed that the organic solvent (component A) penetrates into the adhesive remaining on the wafer, causing it to swell, thereby generating stress on the adhesive surface and promoting adhesive peeling. Furthermore, it is believed that the use of a specific surfactant (component B) in combination with the cleaning composition facilitates penetration into the adhesive, thereby promoting adhesive peeling. From the perspective of adsorbing an appropriate amount of organic solvent (component A) to the adhesive surface, it is believed that there is an appropriate amount of the specific surfactant (component B) to be used in combination. However, the present disclosure need not be construed as being limited to this mechanism.

[0019] [Organic solvent (component A)] The organic solvent (hereinafter also referred to as "Component A") contained in the cleaning composition of the present disclosure includes, for example, an organic solvent containing at least one selected from glycol ethers (Component A1), hydrocarbons (Component A2), and pyrrolidone compounds (Component A3). Component A may consist of one type or a combination of two or more types. The total content of glycol ethers (Component A1), hydrocarbons (Component A2), and pyrrolidone compounds (Component A3) in Component A is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass.

[0020] <Glycol ether (ingredient A1)> In one or more embodiments, the glycol ether (hereinafter also referred to as "Component A1") may contain a compound represented by the following formula (I) from the viewpoint of improving the removability of the adhesive. The content of the compound represented by the following formula (I) in Component A1 is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass. RO-(AO) n -H (I)

[0021] In the above formula (I), R represents a hydrocarbon group having 1 to 6 carbon atoms, AO represents an ethyleneoxy group (EO) or a propyleneoxy group (PO), and n is the number of moles of AO added, which is a number of 1 to 3. In the above formula (I), from the viewpoint of improving the removability of the adhesive, R is preferably a phenyl group or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. From the same viewpoint, AO is preferably an ethyleneoxy group (EO). From the same viewpoint, n is preferably 1 to 3, more preferably 1 or 2.

[0022] Examples of the compound represented by formula (I) include monophenyl ethers such as ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether; and monoalkyl ethers having an alkyl group of 1 to 6 carbon atoms, such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether. Among these, from the viewpoint of improving adhesive removability, preferred compounds represented by formula (I) include monoalkyl ethers having an alkyl group of 1 to 6 carbon atoms, such as ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether. Examples of the compound represented by formula (I) include at least one selected from ethylene glycol monobutyl ether (butyl glycol), diethylene glycol monoethyl ether (ethyl diglycol), diethylene glycol monohexyl ether (hexyl diglycol), and diethylene glycol monobutyl ether (BDG).

[0023] <Hydrocarbons (component A2)> In one or more embodiments, the hydrocarbon (hereinafter also referred to as "component A2") may be, from the viewpoint of improving the removability of the adhesive, an organic solvent such as an alicyclic hydrocarbon or an aromatic hydrocarbon. Examples of the alicyclic hydrocarbon include cycloalkanes such as cyclohexane. Examples of the aromatic hydrocarbon include toluene, ethylbenzene, xylene, and mesitylene (1,3,5-trimethylbenzene).

[0024] From the viewpoint of improving the removability of the adhesive, the number of carbon atoms in component A2 is preferably 5 or more, more preferably 6 or more, and from the same viewpoint, it is preferably 14 or less, more preferably 12 or less, even more preferably 10 or less, and even more preferably 9 or less. When component A2 is an alicyclic hydrocarbon, the number of carbon atoms in component A2 is preferably 5 or more and 14 or less, more preferably 10 or less, and even more preferably 8 or less, from the same viewpoint. When component A2 is an aromatic hydrocarbon, the number of carbon atoms in component A2 is, from the same viewpoint, preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more, and is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.

[0025] <Pyrrolidone compound (ingredient A3)> In one or more embodiments, the pyrrolidone compound (hereinafter also referred to as "component A3") may be a compound represented by the following formula (II), from the viewpoint of improving adhesive removability.

[0026] [ka]

[0027] In the above formula (II), from the viewpoint of improving the removability of the adhesive, R 1 , R 2 , R 3 , R 4 are each independently preferably a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydroxyl group, and R 1 , R2 , R 3 , R 4 It is more preferable that any one of the above is a hydrocarbon group having 1 to 8 carbon atoms, even more preferable that it is a hydrocarbon group having 1 to 6 carbon atoms, and even more preferable that it is any one of a methyl group, an ethyl group, and a vinyl group.

[0028] Examples of the compound represented by formula (II) include 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, 3-hydroxypropyl-2-pyrrolidone, 4-hydroxy-2-pyrrolidone, 4-phenyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. From the viewpoint of improving the removability of the adhesive, the compound represented by formula (II) is preferably at least one selected from 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-octyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone, more preferably at least one selected from 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, and 1-vinyl-2-pyrrolidone, and even more preferably N-methyl-2-pyrrolidone (NMP).

[0029] From the viewpoint of improving the removability of the adhesive, component A may be at least one selected from ethylene glycol monobutyl ether (butyl glycol), diethylene glycol monoethyl ether (ethyl diglycol), diethylene glycol monohexyl ether (hexyl diglycol), diethylene glycol monobutyl ether (BDG), cyclohexane, and N-methyl-2-pyrrolidone (NMP). From the viewpoint of improving the removability of the adhesive, Component A is preferably Component A1 alone or a combination of Component A1 and Component A2.

[0030] The content of Component A in the cleaning composition of the present disclosure is 90% by mass or more, preferably 94% by mass or more, and more preferably 95% by mass or more, from the viewpoints of improving adhesive removability and stability as a cleaning composition. Also, from the viewpoints of improving adhesive removability and stability as a cleaning composition, it is 99.97% by mass or less, preferably 99.5% by mass or less, more preferably 99.3% by mass or less, and even more preferably 99.1% by mass or less. More specifically, the content of Component A in the cleaning composition of the present disclosure is 90% by mass or more and 99.97% by mass or less, preferably 90% by mass or more and 99.5% by mass or less, more preferably 90% by mass or more and 99.3% by mass or less, and even more preferably 95% by mass or more and 99.1% by mass or less. When Component A is a combination of two or more types, the content of Component A refers to the total content of those components.

[0031] In the present disclosure, the "content of each component in the detergent composition" refers to the content of each component at the time of cleaning, i.e., at the time when the detergent composition is first used for cleaning. In one or more embodiments, the content of each component in the cleaning composition of the present disclosure can be considered to be the blending amount of each component in the cleaning composition of the present disclosure.

[0032] [Surfactant (ingredient B)] In one or more embodiments, the surfactant contained in the cleaning composition of the present disclosure (hereinafter also referred to as "Component B") is at least one selected from a fluorine-based surfactant (Component B1) and a silicone-based surfactant (Component B2). Component B may be a single type or a combination of two or more types.

[0033] <Fluorosurfactant (ingredient B1)> The fluorosurfactant (hereinafter referred to as "component B1") may be a surfactant having a perfluoroalkyl group, from the viewpoint of improving the removability of the adhesive. Commercially available fluorosurfactants may be used. Examples of commercially available fluorosurfactants include Surflon (registered trademark) S661, S647, and S651 from AGC Seimi Chemical Co., Ltd.

[0034] <Silicone surfactant (ingredient B2)> The silicone surfactant (hereinafter also referred to as "component B2") may be a polyether-modified silicone from the viewpoint of improving adhesive removability. Examples of polyether-modified silicones include linear polyether-modified silicones, linear alkyl-co-modified polyether-modified silicones, branched polyether-modified silicones, and branched alkyl-co-modified polyether-modified silicones. Of these, linear polyether-modified silicones are preferred from the viewpoint of improving adhesive removability, and examples thereof include polyoxyethylene-methylpolysiloxane copolymers such as PEG-12 dimethicone.

[0035] From the viewpoint of improving the removability of the adhesive, the HLB of component B2 is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and is preferably 8 or less, more preferably 7 or less, and even more preferably 6 or less. More specifically, the HLB of component B is preferably 2 or more and 8 or less, more preferably 3 or more and 7 or less, and even more preferably 4 or more and 6 or less. In the present disclosure, the HLB of a surfactant is a value determined by the Griffin method.

[0036] The content of Component B in the cleaning composition of the present disclosure is 0.03% by mass or more, preferably 0.075% by mass or more, more preferably 0.25% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 0.75% by mass or more, from the viewpoint of improving adhesive removability and the stability of the cleaning composition. It is 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less, from the viewpoint of improving adhesive removability and the stability of the cleaning composition. More specifically, the content of Component B in the cleaning composition of the present disclosure is 0.03% by mass or more and 5% by mass or less, preferably 0.075% by mass or more and 4% by mass or less, more preferably 0.25% by mass or more and 3% by mass or less, even more preferably 0.5% by mass or more and 2% by mass or less, and even more preferably 0.75% by mass or more and 2% by mass or less. When Component B is a combination of two or more types, the content of Component B refers to the total content of those types.

[0037] [Water (component C)] In one or more embodiments, the cleaning composition of the present disclosure may contain no water or may contain 10 mass% or less of water. In one or more embodiments, examples of water (hereinafter also referred to as "component C") include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0038] When the cleaning composition of the present disclosure contains water (component C), the content of component C in the cleaning composition of the present disclosure can be the remainder excluding components A, B, and the optional components described below. Specifically, from the viewpoint of improving adhesive removability, the content of component C in the cleaning composition of the present disclosure is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass (i.e., none).

[0039] [Other ingredients] The cleaning composition of the present disclosure may further contain water (component C) or other components as needed, in addition to the components A and B. Examples of other components include components that are typically used in cleaning agents, such as solvents other than component A, alkaline agents, amines, surfactants other than component B, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents.

[0040] In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of at least one hydroxylamine compound selected from hydroxylamine and hydroxylamine salts. For example, the content of the hydroxylamine compound in the cleaning composition of the present disclosure is preferably less than 1% by mass, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure is preferably substantially free of a basic compound. For example, the content of a basic compound in the cleaning composition of the present disclosure is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of chain amine compounds having a weight-average molecular weight of 95 g / mol or more. For example, the content of chain amine compounds having a weight-average molecular weight of 95 g / mol or more in the cleaning composition of the present disclosure is preferably less than 0.1% by mass, more preferably 0.05% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of chain amine compounds having a weight-average molecular weight of 90 g / mol or less. For example, the content of chain amine compounds having a weight-average molecular weight of 90 g / mol or less in the cleaning composition of the present disclosure is preferably less than 0.5% by mass, more preferably 0.1% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of a cyclic amine compound. For example, the content of the cyclic amine compound in the cleaning composition of the present disclosure is preferably less than 0.1% by mass, more preferably 0.05% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of 1,1,1,3,3-pentafluorobutane. For example, the content of 1,1,1,3,3-pentafluorobutane in the cleaning composition of the present disclosure is preferably less than 70% by mass, more preferably 50% by mass or less, even more preferably 10% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of at least one solvent selected from isopropanolamine, monoethanolamine, and N-substituted ethanolamine. For example, the content of the solvent in the cleaning composition of the present disclosure is preferably less than 3% by mass, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning composition of the present disclosure may be substantially free of an etchant. For example, the content of the etchant in the cleaning composition of the present disclosure is preferably less than 0.1% by mass, more preferably 0.05% by mass or less, and even more preferably 0% by mass.

[0041] [Method of manufacturing the cleaning composition] In one or more embodiments, the cleaning composition of the present disclosure can be produced by blending the components A to B and, if necessary, the optional components described above (component C, other components) using a known method. For example, the cleaning composition of the present disclosure can be produced by blending at least the components A to B. Accordingly, the present disclosure relates to a method for producing a cleaning composition, which includes blending at least the components A to B. In the present disclosure, "blending" includes mixing the components A to B and, if necessary, the optional components described above (component C, other components) simultaneously or in any order. In the method for producing a cleaning composition of the present disclosure, the preferred amount of each component to be blended can be the same as the preferred content of each component in the cleaning composition of the present disclosure described above.

[0042] In one or more embodiments, the cleaning composition of the present disclosure can be used to remove adhesive remaining on a wafer after the wafer, which has been adhesively bonded to a fixing member, is separated from the fixing member. That is, in one or more embodiments, the cleaning composition of the present disclosure is an adhesive remover (hereinafter, also referred to as the "adhesive remover of the present disclosure").

[0043] [Items to be cleaned] In one or more embodiments, the cleaning composition or adhesive remover of the present disclosure is used to remove an adhesive from a substrate (wafer) to which an adhesive is attached. That is, in one aspect, the present disclosure relates to use of the cleaning composition or adhesive remover of the present disclosure for removing an adhesive from a substrate to which an adhesive is attached. An example of the object to be cleaned is a substrate (wafer) with an adhesive attached. In one or more embodiments, the substrate may be a semiconductor substrate. Examples of the semiconductor substrate include wafers such as silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. In one or more embodiments, the substrate may be a substrate having pads and / or lands that are used for bonding and mounting. Examples of materials for the pads and lands include metals such as gold and copper. In one or more embodiments, the substrate (wafer) to which an adhesive is attached may be a wafer that has been adhesively bonded to a fixing member and then separated from the fixing member. In one or more embodiments, the wafer that has been separated from the fixing member is a substrate having metal pads to which an adhesive is attached. Accordingly, in one aspect, the present disclosure relates to the use of a cleaning composition of the present disclosure as a cleaning agent for removing adhesive remaining on a wafer that has been adhesively bonded to a fixing member and then separated from the fixing member. In another aspect, the present disclosure relates to the use of an adhesive remover of the present disclosure as a remover for removing adhesive remaining on a wafer that has been adhesively bonded to a fixing member and then separated from the fixing member. In one or more embodiments, the wafer that has been adhesively fixed to a fixing member has been subjected to a heat treatment at a temperature of 230°C or higher. In one or more embodiments, the heat treatment may be a heat treatment in the processing step described below. In one or more embodiments, the substrate (wafer) having an adhesive attached thereto may be a substrate having an adhesive attached thereto used in the manufacturing process of three-dimensional integrated circuits (3DIC). Accordingly, in one aspect, the present disclosure relates to the use of the cleaning composition of the present disclosure as a cleaning agent for removing adhesives used in the manufacturing process of three-dimensional integrated circuits. In another aspect, the present disclosure relates to the use of the adhesive remover of the present disclosure as a remover for removing adhesives used in the manufacturing process of three-dimensional integrated circuits. In one or more embodiments, the substrate (wafer) to which the adhesive is attached has undergone a heat treatment at a temperature of 230° C. or higher. In one or more embodiments, the heat treatment may be a heat treatment in the processing step described below.

[0044] [Method of manufacturing semiconductor substrate] In one aspect, the present disclosure relates to a method for producing a semiconductor substrate (hereinafter also referred to as the "semiconductor substrate production method of the present disclosure"), comprising the steps of: (1) bonding a wafer to a fixing member with an adhesive; (2) polishing the surface of the wafer opposite the surface bonded to the fixing member; (3) processing the polished surface of the wafer; (4) separating the processed wafer from the fixing member; and (5) removing any adhesive remaining on the separated wafer with a cleaning agent, wherein the cleaning agent is a cleaning agent composition containing an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, and the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less. In one or more embodiments, the cleaning agent used in step (5) is the cleaning agent composition of the present disclosure described above.

[0045] The method for manufacturing a semiconductor substrate according to the present disclosure will be described with reference to Fig. 1 and Fig. 2. Fig. 1 is a flowchart showing the steps of the method for manufacturing a semiconductor substrate according to the present disclosure. Fig. 2 is a schematic diagram for explaining the steps of one embodiment of the method for manufacturing a semiconductor substrate according to the present disclosure.

[0046] <Process (1): Adhesion process> Step (1) is a step (adhesion step) of adhering a wafer 3 to a fixing member 1 with an adhesive 2 (step S1). In one or more embodiments, step (1) includes a step (1-1) of applying an adhesive to the surface of the wafer or the fixing member to form an adhesive layer, and a step (1-2) of bonding the wafer and the fixing member together via the adhesive layer and performing a heat treatment to bond them.

[0047] Examples of the wafer used in step (1) include a silicon wafer or a glass wafer having a diameter of 100 to 500 mm and a thickness of 50 to 2,000 μm. In one or more embodiments, the wafer used in step (1) is a substrate having metal pads.

[0048] The fixing member used in step (1) is not particularly limited, but examples thereof include substrates such as silicon wafers and glass plates having a diameter of 100 to 500 mm and a thickness of 50 to 20,000 μm.

[0049] The adhesive used in step (1) is not particularly limited as long as it can bond the substrate to the fixing member, has durability sufficient to withstand the polishing step and the processing step, and allows the substrate to be easily separated from the fixing member in the separation step, but examples thereof include adhesives used in the manufacturing process of 3DIC. Examples of adhesives used in the manufacturing process of 3DIC include polysiloxane-based, acrylic-based, or methacrylic-based adhesives (adhesive compositions). Specifically, examples include the adhesive compositions described in JP 2021-161196 A. In one or more embodiments, the adhesive composition used in step (1) may contain a polysiloxane, an acrylic acid ester, or a methacrylic acid ester as an adhesive component, and may further contain a platinum group metal catalyst, a release agent component, a solvent, etc. The viscosity of the adhesive composition used in step (1) can be adjusted by appropriately changing the concentration of the components contained therein depending on the application method, film thickness, etc.

[0050] In the step (1-1), the method for applying the adhesive (adhesive composition) is not particularly limited, but examples thereof include spin coating. The thickness of the coating layer (adhesive layer) of the adhesive (adhesive composition) is, for example, 5 to 500 μm. In one or more embodiments, step (1-1) includes bonding the surface of the wafer having the metal pads to the fixing member with an adhesive.

[0051] In the step (1-2), the temperature for the heat treatment is, for example, 80° C. or higher, and is preferably 150° C. or lower in order to prevent the adhesive from being excessively hardened. The heat treatment time may be, for example, 30 seconds or more, and is preferably 10 minutes or less from the viewpoint of suppressing deterioration of the adhesive layer and other members. Heating can be carried out using a hot plate, an oven, or the like. The thickness of the adhesive layer after heat treatment is, for example, 5 μm or more and 100 μm or less.

[0052] <Process (2): Polishing process> Step (2) is a step (polishing step) of polishing the surface (back surface) 3a of the wafer 3 opposite to the surface bonded to the fixing member 1 (step S2). Examples of the polishing method include mechanical polishing using abrasive grains and chemical mechanical polishing. In step (2), the thickness of the polished wafer (thinned wafer) is preferably 200 μm or less, for example, 50 μm to 200 μm.

[0053] <Process (3): Processing process> Step (3) is a step (processing step) of processing the polished surface (rear surface of the thinned wafer) 3a of the wafer 3 (step S3). In one or more embodiments, step (3) may be an electrode formation step, a metal wiring formation step, a protective film formation step, etc. Examples of such steps include conventionally known processing steps such as metal sputtering for forming electrodes, wet etching, resist application, pattern formation, resist stripping, dry etching, metal plating, silicon etching for forming through-silicon vias (TSVs), and oxide film formation on silicon surfaces. In one or more embodiments, the processing in step (3) is performed at a high temperature of 150° C. or higher. When forming electrodes such as TSVs, a heat treatment at 250° C. or higher and 350° C. or lower may be performed.

[0054] <Step (4): Separation step> Step (4) is a step (separation step) of separating the processed wafer 3 from the fixing member 1 (step S4). Examples of the separation method include solvent peeling, laser peeling, and mechanical peeling.

[0055] <Step (5): Cleaning step> Step (5) is a step (cleaning step) of removing the adhesive (adhesive residue) 2a remaining on the separated wafer 3 with a cleaning agent (step S5). In one or more embodiments, the separated wafer is a substrate (the object to be cleaned described above) to which an adhesive has adhered, such as a substrate having an adhesive adhered to a metal pad. The cleaning agent used in step (5) may be the cleaning agent composition of the present disclosure described above. An example of a method for removing adhesives is immersion cleaning. The immersion conditions for immersion cleaning are, for example, a cleaning agent temperature of 40°C or higher and 70°C or lower, and a immersion time of 1 minute or higher and 60 minutes or lower. Ultrasonic vibrations are preferably applied to the cleaning agent, for example, at frequencies of 25 to 50 kHz, and more preferably 35 to 45 kHz from the viewpoint of suppressing damage to the substrate. After cleaning, the substrate may be washed with water or rinsed with alcohol and then dried.

[0056] In one or more embodiments, step (5) is a step of removing the adhesive remaining on the separated wafer with an adhesive remover. Examples of the adhesive remover used in step (5) include the adhesive remover of the present disclosure described above. That is, in one or more embodiments, the method for manufacturing a semiconductor substrate of the present disclosure is a method for manufacturing a semiconductor substrate that includes the steps of: (1) bonding a wafer to a fixing member with an adhesive; (2) polishing the surface of the wafer opposite to the surface bonded to the fixing member; (3) processing the polished surface of the wafer; (4) separating the processed wafer from the fixing member; and (5) removing any adhesive remaining on the separated wafer with the adhesive remover of the present disclosure.

[0057] [Cleaning method] In one aspect, the present disclosure relates to a cleaning method (hereinafter also referred to as the "cleaning method of the present disclosure") that includes a step (cleaning step) of removing adhesive remaining on the wafer with a cleaning agent after separating the wafer, the adhesive being bonded to a holding member with an adhesive, from the holding member, the cleaning agent being a cleaning agent composition containing an organic solvent (component A) and a surfactant (component B), where component B is at least one surfactant selected from a fluorine-based surfactant and a silicone-based surfactant, the content of component A being 90% by mass or more and 99.97% by mass or less, and the content of component B being 0.03% by mass or more and 5% by mass or less. In one or more embodiments, the cleaning agent is the cleaning agent composition of the present disclosure described above. In the cleaning method of the present disclosure, the adhesive can be removed by the same method as the removal method in step (5) in the semiconductor substrate manufacturing method of the present disclosure described above. In one or more embodiments of the cleaning method of the present disclosure, the wafer bonded to the fixing member with an adhesive has been subjected to a heat treatment at a temperature of preferably 230°C or higher, more preferably 270°C or higher. Heat treatment at a temperature of 230°C or higher includes, for example, a heat treatment for bonding a device such as a semiconductor chip and a substrate on which another circuit is formed to a substrate on which a circuit is formed, using solder or metal fine particles. The heat treatment step may be performed after the processing step of step (3) and before step (4). In one or more embodiments, the object to be cleaned in the cleaning method of the present disclosure may be a wafer that has undergone steps (1) to (4) in the semiconductor substrate manufacturing method of the present disclosure.

[0058] In one or more embodiments, the cleaning step in the cleaning method of the present disclosure is a step (removal step) of removing the adhesive remaining on the wafer with an adhesive remover after separating the wafer, which has been adhesively bonded to a fixing member, from the fixing member. Examples of the adhesive remover used in the removal step include the adhesive remover of the present disclosure described above. That is, in one or more embodiments, the cleaning method of the present disclosure is an adhesive removal method that includes a step of removing the adhesive remaining on the wafer with the adhesive remover of the present disclosure after separating the wafer, which is adhesively bonded to a fixing member, from the fixing member.

[0059] [kit] In one aspect, the present disclosure relates to a kit for use in either the cleaning method of the present disclosure or the semiconductor substrate manufacturing method of the present disclosure (hereinafter also referred to as the "kit of the present disclosure"). In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. The kit of the present disclosure allows for the production of a cleaning composition that is excellent in adhesive removal ability.

[0060] In one or more embodiments, the kit of the present disclosure includes a kit (two-liquid cleaning composition) that contains a solution containing component A (first liquid) and a solution containing component B (second liquid) in a mutually unmixed state, and the first liquid and the second liquid are mixed at the time of use. After the first liquid and the second liquid are mixed, they may be diluted with component C (water) as needed. Each of the first liquid and the second liquid may contain the above-mentioned optional components as needed. [Example]

[0061] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0062] 1. Preparation of cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 The components shown in Table 1 were blended in the amounts (mass %, active ingredient) shown in Table 1 and mixed by stirring to prepare the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5.

[0063] The cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 were prepared using the following materials. (Component A) BDG (butyl diglycol) [Nippon Nyukazai Co., Ltd. (ingredient A1)] Cyclohexane [Fujifilm Wako Pure Chemical Industries, Ltd., (Component A2)] N-methylpyrrolidone (NMP) [Fujifilm Wako Pure Chemical Industries, Ltd., (Component A3)] Butyl glycol [Nippon Nyukazai Co., Ltd. (ingredient A1)] Ethyl diglycol [Fujifilm Wako Pure Chemical Industries, Ltd., (ingredient A1)] Hexyl diglycol [Nippon Nyukazai Co., Ltd. (ingredient A1)] (Component B) Fluorosurfactant 1 [AGC Seiwa Chemical Co., Ltd., Surflon S-611] Fluorosurfactant 2 [AGC Seiwa Chemical Co., Ltd., Surflon S-647] Fluorosurfactant 3 [AGC Seiwa Chemical Co., Ltd., Surflon S-651] Silicone surfactant (PEG12-dimethicone) [Polyoxyethylene-methylpolysiloxane copolymer, Dow Chemical Co., DOWSIL SH 3775 M FLUID, HLB=5] (Non-ingredient B) Polyoxyethylene (9) lauryl ether [Kao Corporation, Emulgen 109P] (Component C) Water [pure water of 1 μS / cm or less produced using the Organo Corporation G-10DSTSET water purification system]

[0064] 2. Evaluation of the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 The prepared cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 were evaluated as follows.

[0065] [Evaluation of cleaning ability (adhesive removal)] A 200 mL beaker was charged with 200 mL of each of the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 and heated to 60°C. Test pieces with adhesive residues on their metal pads were immersed in the cleaning composition at 60°C for 30 minutes while being exposed to ultrasound (40 kHz, 360 W) using an ultrasonic cleaner (ASU-20M, manufactured by AS ONE Corporation). The test pieces were then removed from the cleaning composition and rinsed with ethanol (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) for approximately 20 seconds at room temperature, and then allowed to dry at room temperature. After visually inspecting the test pieces for residual adhesive, the test pieces were visually inspected for residual adhesive at 20x magnification using an optical microscope, "Digital Microscope VHX-2000" (manufactured by Keyence Corporation). The cleaning rate was calculated using the following formula based on the number of metal pads from which the adhesive had been removed, and the cleaning ability (adhesive removability) was evaluated based on the following evaluation criteria. The results are shown in Table 1. Cleaning rate = (Number of pads with adhesive before cleaning - Number of pads with adhesive after cleaning) / (Number of pads with adhesive before cleaning) x 100 <Evaluation criteria> A: Cleaning rate of 90% or more B: Cleaning rate: 80% to less than 90% C: Cleaning rate 70% or more but less than 80% D: Cleaning rate less than 70% The test piece used had metal pads with adhesive on them. The test piece was 15 mm x 15 mm in size, with adhesive (adhesive layer) covering the entire surface of the 450 μm diameter metal pads arranged at a pitch of 900 μm. Specifically, the 450 μm diameter gold metal pads were arranged in a grid pattern with 450 μm intervals. An acrylic adhesive was used as the adhesive. The adhesive layer was formed by applying the adhesive to the entire surface of the metal pads and then heating it at 260°C for 20 minutes. The film thickness of the adhesive layer after heating was 50 μm.

[0066] [Evaluation of Al electrode damage] 100 mL of each of the cleaning compositions of Examples 1 to 12 and Comparative Examples 1 to 5 was added to a 100 mL beaker and heated to 60°C. Test pieces were immersed in the cleaning composition at 60°C for 60 minutes while being exposed to ultrasound (40 kHz, 360 W) using an ultrasonic cleaner (ASU-20M, manufactured by AS ONE Corporation). The test pieces were then removed from the cleaning composition and rinsed with ethanol (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) for approximately 20 seconds at room temperature, and then allowed to dry at room temperature. Using an optical microscope, "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), the test pieces after the cleaning test were visually inspected at 100x magnification, and damage to the Al electrode was evaluated based on the following evaluation criteria. The results are shown in Table 1. The test piece was 15 mm x 15 mm in size and had 3 mm x 2.5 mm Al electrodes tightly spaced on a silicon wafer. <Evaluation criteria> A: No discoloration is observed on the electrodes B: No discoloration of the electrode, but slight reduction in gloss C: No discoloration of the electrode, but gloss has decreased D: Discoloration of the electrode is observed

[0067] [Table 1]

[0068] As shown in Table 1, the cleaning compositions of Examples 1 to 12 were found to be superior in adhesive removability to Comparative Example 1, which did not contain Component B, Comparative Example 2, which used polyoxyethylene lauryl ether (non-Component B) as a surfactant, Comparative Example 3, which contained less than 0.03 mass% of Component B, and Comparative Examples 4 and 5, which contained less than 90 mass% of Component A. It was also found that the cleaning compositions of Examples 1 to 12 were able to suppress damage to Al electrodes. [Industrial Applicability]

[0069] According to the present disclosure, a cleaning composition having excellent adhesive removability can be provided. Furthermore, use of the cleaning composition of the present disclosure can improve productivity of semiconductor substrates. [Explanation of symbols]

[0070] 1 Fixing member 2. Adhesive 2a Adhesive residue 3 wafers 3a Polished and processed surface of wafer

Claims

1. A cleaning agent composition for removing adhesive residue from a wafer, It contains an organic solvent (component A) and a surfactant (component B), Component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants. The content of component A is 90% by mass or more and 99.97% by mass or less. A cleaning agent composition for adhesives, wherein the content of component B is 0.03% by mass or more and 5% by mass or less.

2. The cleaning agent composition for adhesives according to claim 1, wherein component A comprises at least one selected from glycol ethers, hydrocarbons, and pyrrolidone compounds.

3. The adhesive cleaning agent composition according to claim 2, wherein the glycol ether comprises a compound represented by the following formula (I). RO-(AO)n-H (I) In the above formula (I), R represents a hydrocarbon group having 1 to 6 carbon atoms, AO represents an ethylene oxy group (EO) or a propylene oxy group (PO), and n is the number of moles of AO added, which is between 1 and 3.

4. The cleaning agent composition for adhesives according to claim 1, wherein the HLB of the silicone-based surfactant is 2 or more and 8 or less.

5. The cleaning agent composition for adhesives according to claim 1, wherein it does not contain water or contains 10% by mass or less of water.

6. The cleaning agent composition for adhesives according to claim 1, wherein the content of a basic compound is 1% by mass or less.

7. The adhesive cleaning agent composition for adhesives according to any one of claims 1 to 6, wherein the adhesive is an adhesive used in the manufacturing process of a three-dimensional integrated circuit.

8. An adhesive remover for removing adhesive residue from a wafer, It contains an organic solvent (component A) and a surfactant (component B), Component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants. The content of component A is 90% by mass or more and 99.97% by mass or less. An adhesive remover having a content of component B of 0.03% by mass or more and 5% by mass or less.

9. (1) A step of bonding the wafer to the fixing member with an adhesive, (2) A step of polishing the side of the wafer opposite to the side that is bonded to the fixing member, (3) A process for processing the polished surface of the wafer, (4) A step of separating the processed wafer from the fixing member, (5) A step of removing the adhesive remaining on the separated wafer with a cleaning agent, A method for manufacturing a semiconductor substrate, including The cleaning agent composition comprises an organic solvent (component A) and a surfactant (component B), wherein component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants, the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less. A method for manufacturing semiconductor substrates.

10. (1) A step of bonding the wafer to the fixing member with an adhesive, (2) A step of polishing the side of the wafer opposite to the side that is bonded to the fixing member, (3) A process for processing the polished surface of the wafer, (4) A step of separating the processed wafer from the fixing member, (5) A step of removing the adhesive remaining on the separated wafer with an adhesive remover, A method for manufacturing a semiconductor substrate, including The adhesive remover contains an organic solvent (component A) and a surfactant (component B), wherein component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants, the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less. A method for manufacturing semiconductor substrates.

11. The process includes separating a wafer bonded to a fixing member with adhesive from the fixing member, and then removing any remaining adhesive from the wafer with a cleaning agent. The cleaning agent composition comprises an organic solvent (component A) and a surfactant (component B), wherein component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants, the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less. Cleaning method.

12. The cleaning method according to claim 11, wherein the wafer fixed to the fixing member with adhesive has been subjected to a heat treatment at a temperature of 230°C or higher.

13. The process includes separating a wafer bonded to a fixing member with adhesive from the fixing member, and then removing any remaining adhesive from the wafer using an adhesive remover. The adhesive remover contains an organic solvent (component A) and a surfactant (component B), wherein component B is at least one surfactant selected from fluorine-based surfactants and silicone-based surfactants, the content of component A is 90% by mass or more and 99.97% by mass or less, and the content of component B is 0.03% by mass or more and 5% by mass or less. Method for removing adhesive.

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