Cleaning agent composition for adhesive

Abstract

To provide a cleaning agent composition for an adhesive with excellent removability of the adhesive.SOLUTION: A cleaning agent composition for an adhesive is for removing residual adhesive from a wafer. The cleaning agent composition for an adhesive contains a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine (component C) having a linear alkanol group. The cleaning agent composition for an adhesive does not contain water or contains equal to or less than 10% by mass of water. A mass ratio A / B of the content of the component A to the content of the component B is 1.7 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an adhesive cleaning composition, a method for manufacturing and cleaning a semiconductor substrate using the same, and an adhesive remover and a cleaning method 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 being thinned, a 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 separation from the fixing member, which can cause problems in subsequent processes. Therefore, a cleaning process is performed to remove the adhesive remaining on the wafer, and various cleaning compositions for use in the cleaning process have been developed.

[0003] For example, Patent Document 1 discloses a rework solvent (cleaning agent) 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, and in the examples, a rework solvent comprising monoethanolamine, dipropylene glycol dimethyl ether, and N-methyl-2-pyrrolidone is disclosed. Patent Document 2 proposes a cleaning composition containing a hydrocarbon having 9 to 16 carbon atoms and at least one selected from specific ether compounds or ester compounds in specific ratios as a cleaning composition for removing wax, adhesives, etc. In the examples of this document, a cleaning liquid composition is disclosed that contains a component mainly composed of an alkylbenzene having 9 to 11 carbon atoms, a component mainly composed of dimethylnaphthalene and an alkylnaphthalene having 12 to 13 carbon atoms, normal dodecane, and diethylene glycol monobutyl ether. Patent Document 3 proposes a detergent composition for removing wax, etc., which contains 1 to 20 mass% of saturated aliphatic hydrocarbons and / or unsaturated aliphatic hydrocarbons having 8 to 20 carbon atoms, 5 to 40 mass% of a specific glycol ether, 1 to 20 mass% of a specific nonionic surfactant, and 1 to 30 mass% of an alkanolamine having a branched carbon chain. As a comparative example, the same document discloses a detergent composition consisting of tetradodecene, diethylene glycol mono-2-ethylhexyl ether, hexyl diglycol, trialkylene glycol monobutyl ether, triethylene glycol monobutyl ether, triethanolamine, and 53 mass% of water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2016 / 021646 issue [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-74777 [Patent Document 3] Japanese Patent Application Laid-Open No. 2013-10888 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. If the adhesive changes in quality due to heating, it tends to be difficult to remove. Cleaning compositions are required to have excellent adhesive removal (cleaning properties). The cleaning compositions proposed in Patent Documents 1 to 3 have room for improvement in terms of the ability to remove adhesive remaining on wafers.

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

[0007] In one aspect, the present disclosure relates to a cleaning composition for removing adhesives remaining on wafers, the cleaning composition for adhesives containing a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and containing no water or a water content of 10 mass% or less, and wherein the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

[0008] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate, comprising 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 the adhesive remaining on the separated wafer with a cleaning agent, wherein the cleaning agent is a cleaning agent composition that contains a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and that is water-free or contains 10 mass% or less of water, and has a mass ratio A / B of 1.7 or less of the content of component A to the content of component B.

[0009] In one aspect, the present disclosure relates to a cleaning method including a step of removing, with a cleaning agent, the adhesive remaining on the wafer 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 a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and which is either water-free or contains 10 mass % or less of water, and in which the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

[0010] In one aspect, the present disclosure relates to an adhesive remover for removing adhesive remaining on a wafer, the adhesive remover comprising a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), the adhesive remover containing no water or containing 10 mass % or less of water, and having a mass ratio A / B of the content of component A to the content of component B of 1.7 or less.

[0011] In one aspect, the present disclosure relates to a cleaning method including a step of removing adhesive remaining on a wafer with an adhesive remover after separating a wafer, which has been adhesively bonded to a fixing member, from the fixing member, wherein the adhesive remover contains a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and is water-free or contains 10 mass % or less of water, and has a mass ratio A / B of the content of component A to the content of component B of 1.7 or less. [Effects of the Invention]

[0012] According to the present disclosure, it is possible to provide an adhesive cleaning composition that has excellent adhesive removability, a semiconductor substrate manufacturing method and cleaning method using the same, and an adhesive remover and a cleaning method using the same. [Brief explanation of the drawings]

[0013] [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

[0014] The present disclosure is based on the finding that adhesives can be efficiently removed by using a cleaning composition or adhesive remover that contains a glycol ether, a hydrocarbon, and an alkanolamine having a linear alkanol group, and that has a water content of 0 mass % or 10 mass % or less.

[0015] In one aspect, the present disclosure relates to a cleaning composition for removing adhesives remaining on wafers, the cleaning composition for adhesives containing a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and either containing no water or containing 10 mass% or less of water, and having a mass ratio A / B of the content of component A to the content of component B of 1.7 or less (hereinafter also referred to as the "cleaning composition of the present disclosure"). In another aspect, the present disclosure relates to an adhesive remover for removing adhesive remaining on a wafer, the adhesive remover containing a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and either containing no water or containing 10 mass% or less of water, and having a mass ratio A / B of the content of component A to the content of component B of 1.7 or less (hereinafter also referred to as "the adhesive remover of the present disclosure").

[0016] According to the present disclosure, a cleaning composition and an adhesive remover having excellent adhesive removability can be provided. Furthermore, by using the cleaning composition or adhesive remover of the present disclosure, high-quality semiconductor substrates can be obtained with high yield.

[0017] Although the details of the mechanism by which the cleaning composition and adhesive remover of the present disclosure exert their effects are partially unknown, it is presumed as follows. In the cleaning composition and adhesive remover of the present disclosure, the glycol ether (component A) and hydrocarbon (component B) are thought to penetrate into the adhesive remaining on the wafer, causing it to swell, thereby generating stress on the adhesive surface and promoting adhesive removal. Furthermore, alkanolamine (component C) has difficulty penetrating into the adhesive alone, but when used in combination with glycol ether (component A) and hydrocarbon (component B), it easily penetrates into the adhesive, promoting dissociation of the alkali-soluble resin contained in the adhesive and further promoting adhesive removal by causing repulsion of the charges generated by the dissociation. Furthermore, when the cleaning composition and adhesive remover of the present disclosure do not contain water or contain 10 mass% or less of water, it is believed that the rate at which each component penetrates into the adhesive increases, improving detergency. Furthermore, when the mass ratio A / B of the content of Component A to the content of Component B in the cleaning composition and adhesive remover of the present disclosure is 1.7 or less, it is believed that the components can penetrate more easily into the adhesive, promoting dissociation of the alkali-soluble resin contained in the adhesive and further facilitating the removal of the adhesive by causing repulsion of the charges generated by the dissociation. However, the present disclosure need not be construed as being limited to this mechanism.

[0018] In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure are used to remove adhesive from a wafer having an adhesive attached thereto. That is, in one aspect, the present disclosure relates to the use of the cleaning composition and adhesive remover of the present disclosure for removing adhesive from a wafer having an adhesive attached thereto. Examples of wafers include semiconductor substrates, such as silicon wafers, germanium wafers, gallium arsenide wafers, gallium phosphide wafers, and gallium arsenide aluminum wafers. In one or more embodiments, the wafer may be a substrate having pads and / or lands that are used for bonding and mounting. Examples of adhesives include those that can bond the wafer to the fixing member, have durability that can withstand the polishing and processing steps, and allow the wafer to be easily separated from the fixing member in the separation step. Examples of adhesives include polyimide-based, polysiloxane-based, acrylic-based, and methacrylic-based adhesives (adhesive compositions).

[0019] [Glycol ether (ingredient A)] The glycol ether (hereinafter also referred to as "Component A") contained in the cleaning composition and adhesive remover of the present disclosure may, for example, contain a compound represented by the following formula (I). Component A may be one type or a combination of two or more types. The content of the compound represented by the following formula (I) in Component A 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)

[0020] 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.

[0021] 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 the removability of the adhesive, the compound represented by formula (I) is more preferably at least one selected from ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, and tripropylene glycol monoalkyl ether, each having an alkyl group of 1 to 6 carbon atoms, and even more preferably at least one selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (BDG), and propylene glycol monomethyl ether (PGME). In one or more embodiments, component A has a solubility in water at 20° C. of more than 10% by mass.

[0022] The content of Component A in the cleaning composition and adhesive remover of the present disclosure is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoints of improving adhesive removability and compatibility, and is preferably 65% ​​by mass or less, more preferably 60% by mass or less, from the viewpoint of improving adhesive removability. More specifically, the content of Component A in the cleaning composition and adhesive remover of the present disclosure is preferably 10% by mass or more and 65% by mass or less, more preferably 15% by mass or more and 60% 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 thereof.

[0023] In the present disclosure, the "content of each component in the cleaning composition and adhesive remover" refers to the content of each component at the time of cleaning, i.e., at the time when the cleaning composition and adhesive remover start to be used for cleaning. In one or more embodiments, the content of each component in the cleaning composition and adhesive remover of the present disclosure can be considered to be the blending amount of each component in the cleaning composition and adhesive remover of the present disclosure.

[0024] [Hydrocarbon (Component B)] In one or more embodiments, the hydrocarbon (hereinafter also referred to as "Component B") contained in the cleaning composition and adhesive remover of the present disclosure is a hydrocarbon-based organic solvent. From the viewpoint of improving adhesive removability, hydrocarbons having a cyclic structure are preferred, and organic solvents such as alicyclic hydrocarbons (Component B1) and aromatic hydrocarbons (Component B2) are more preferred. Examples of alicyclic hydrocarbons (Component B1) include cycloalkanes such as cyclohexane. Examples of aromatic hydrocarbons (Component B2) include toluene, ethylbenzene, xylene, and mesitylene (1,3,5-trimethylbenzene). Component B may be used alone or in combination of two or more. The total content of the alicyclic hydrocarbons (Component B1) and aromatic hydrocarbons (Component B2) in Component B is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass.

[0025] From the viewpoint of improving the removability of the adhesive, the number of carbon atoms in component B 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 B is an alicyclic hydrocarbon (component B1), the number of carbon atoms in component B1 is preferably 5 or more and preferably 14 or less, more preferably 10 or less, and even more preferably 8 or less, from the same viewpoint. When component B is an aromatic hydrocarbon (component B2), from the same viewpoint, the number of carbon atoms in component B2 is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and is preferably 14 or less, more preferably 12 or less, even more preferably 10 or less, and even more preferably 9 or less.

[0026] Examples of component B include at least one selected from ethylbenzene, xylene, mesitylene, and cyclohexane, and from the viewpoints of improving adhesive removability, storage stability, availability, and chemical substance regulations, ethylbenzene or xylene is preferred. In one or more embodiments, from the viewpoint of improving the removability of the adhesive, Component B is preferably an aromatic hydrocarbon (Component B2), more preferably an aromatic hydrocarbon having 5 to 14 carbon atoms, even more preferably an aromatic hydrocarbon having 6 to 12 carbon atoms, even more preferably an aromatic hydrocarbon having 7 to 10 carbon atoms, even more preferably an aromatic hydrocarbon having 7 to 9 carbon atoms, and even more preferably at least one selected from ethylenebenzene, xylene, and methylene.

[0027] The content of component B in the cleaning composition and adhesive remover of the present disclosure is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoint of improving adhesive removability, and is preferably 80% by mass or less, more preferably 70% by mass or less, from the viewpoint of compatibility. More specifically, the content of component B in the cleaning composition and adhesive remover of the present disclosure is preferably 15% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% 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 thereof.

[0028] In one or more embodiments, the content of component A and the content of component B in the cleaning composition and adhesive remover of the present disclosure, and the mass ratio A / B (content of component A) / (content of component B), is 1.7 or less, preferably 1.5 or less, more preferably 1.3 or less, even more preferably 1.0 or less, and even more preferably less than 1.0, from the viewpoint of improving adhesive removability. The mass ratio A / B is not particularly limited in its lower limit, but from the same viewpoint, it is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 0.7 or more. From the same viewpoint, the mass ratio A / B is preferably 0.1 or more and 1.7 or less, more preferably 0.1 or more and 1.5 or less, more preferably 0.1 or more and 1.3 or less, even more preferably 0.1 or more and 1.0 or less, and even more preferably 0.1 or more and 1.0 or less.

[0029] [Alkanolamine (ingredient C)] The alkanolamine (amino alcohol) (hereinafter also referred to as "component C") contained in the cleaning composition and adhesive remover of the present disclosure may, for example, contain a compound represented by the following formula (II). Component C may be one type or a combination of two or more types. In one or more embodiments, component C is a compound that does not have a branched carbon chain. The content of the compound represented by the following formula (II) in component C is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass. [ka]

[0030] In the above formula (II), R 1 represents a linear alkanol group having 2 to 4 carbon atoms, and R 2 represents a linear alkanol group having 2 to 4 carbon atoms, a methyl group, or a hydrogen atom; R 3 represents a methyl group or a hydrogen atom. In the above formula (II), R 1 From the viewpoint of improving the removability of the adhesive, R is preferably a linear alkanol group having 2 or 3 carbon atoms. 2 From the same viewpoint, R is preferably a hydrogen atom. 3 From the same viewpoint, is preferably a hydrogen atom.

[0031] Examples of Component C include at least one selected from monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, N-dimethylmonoethanolamine, N-methyldiethanolamine, N-diethylmonoethanolamine, N-ethyldiethanolamine, N-(β-aminoethyl)ethanolamine, and N-(β-aminoethyl)diethanolamine. Among these, from the viewpoint of improving adhesive removability, alkylmonoalkanolamines or monoalkanolamines are preferred, and monoethanolamine is more preferred.

[0032] The content of component C in the cleaning composition and adhesive remover of the present disclosure is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of improving adhesive removability, reducing component damage, and reducing nitrogen content, and is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. More specifically, the content of component C in the cleaning composition and adhesive remover of the present disclosure is preferably 3% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less. When component C is a combination of two or more types, the content of component C refers to the total content of those components.

[0033] [Water (ingredient D)] The cleaning composition and adhesive remover of the present disclosure contain no water or contain 10 mass% or less of water. In one or more embodiments, examples of water (hereinafter also referred to as "component D") include ion-exchanged water, RO water, distilled water, pure water, and ultrapure water.

[0034] The content of component D in the cleaning composition and adhesive remover of the present disclosure can be the remainder excluding components A, B, C, and the optional components described below. Specifically, from the viewpoint of improving adhesive removability, the content of component D in the cleaning composition and adhesive remover 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 essentially 0% by mass (i.e., absent).

[0035] [Other ingredients] The cleaning composition and adhesive remover of the present disclosure may further contain water (component D) or other components as needed, in addition to the components A to C. Examples of other components include components that can be used in ordinary cleaning agents, such as solvents other than component A, alkaline agents other than component C, amines other than component C, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymeric compounds, solubilizers, antioxidants, preservatives, antifoaming agents, and antibacterial agents.

[0036] The cleaning composition and adhesive remover of the present disclosure have excellent adhesive removability without using N-methyl-2-pyrrolidone, a polar solvent with excellent properties. From the viewpoint of exerting adhesive removability effects, the cleaning composition and adhesive remover of the present disclosure preferably contain N-methyl-2-pyrrolidone as another component in an amount of 1% by mass or less, and more preferably 0% by mass (i.e., no N-methyl-2-pyrrolidone is contained).

[0037] In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure may be substantially free of alkanolamines having branched carbon chains. For example, the content of alkanolamines having branched carbon chains in the cleaning composition and adhesive remover 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 (i.e., no alkanolamines). In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure may be substantially free of a nonionic surfactant. For example, the content of nonionic surfactant in the cleaning composition and adhesive remover 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 (i.e., no surfactant is contained). Examples of nonionic surfactants include those obtained by adding any ethylene oxide or propylene oxide to an aliphatic hydrocarbon or aromatic hydrocarbon having 8 to 10 carbon atoms. In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure can be substantially free of aliphatic hydrocarbons having 9 to 16 carbon atoms. For example, the content of aliphatic hydrocarbons having 9 to 16 carbon atoms in the cleaning composition and adhesive remover of the present disclosure is preferably 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass (i.e., no content). In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure may be substantially free of polar organic solvents. For example, the content of polar organic solvents in the cleaning composition and adhesive remover of the present disclosure is preferably less than 5% by mass, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass (i.e., no polar organic solvents are contained). In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure may be substantially free of quaternary ammonium. For example, the content of quaternary ammonium in the cleaning composition and adhesive remover of the present disclosure is preferably less than 3% by mass, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0% by mass (i.e., no quaternary ammonium).

[0038] [Method of manufacturing the cleaning composition and adhesive remover] In one or more embodiments, the cleaning composition and adhesive remover of the present disclosure can be produced by blending the components A to C and, if necessary, the optional components described above (component D and other components) using a known method. For example, the cleaning composition and adhesive remover of the present disclosure can be produced by blending at least the components A to C. Thus, the present disclosure relates to a method for producing a cleaning composition and an adhesive remover, which includes a step of blending at least the components A to C. In the present disclosure, "blending" includes mixing the components A to C and, if necessary, the optional components described above (component D and other components) simultaneously or in any order. In the method for producing the cleaning composition and adhesive remover of the present disclosure, the preferred amount of each component can be the same as the preferred content of each component of the cleaning composition and adhesive remover of the present disclosure described above.

[0039] [Items to be cleaned] An example of the object to be cleaned is a wafer with an adhesive attached. In one or more embodiments, the wafer may be a semiconductor substrate. In one or more embodiments, the semiconductor substrate may be a silicon wafer, a germanium wafer, a gallium-arsenide wafer, a gallium-phosphorus wafer, or a gallium-arsenide-aluminum wafer. In one or more embodiments, the wafer 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 wafer with adhesive attached thereto 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 may be a substrate having a metal pad to which an adhesive has been attached. Accordingly, in one aspect, the present disclosure relates to use of the cleaning composition or adhesive remover 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 one or more embodiments, the wafer that has been adhesively fixed to the 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 wafer having an adhesive attached thereto may be a wafer 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 use of the cleaning composition or adhesive remover of the present disclosure as a cleaning agent for removing adhesives used in the manufacturing process of three-dimensional integrated circuits. In one or more embodiments, the 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 a processing step described below.

[0040] [Method of manufacturing semiconductor substrate] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate (hereinafter also referred to as the "semiconductor substrate manufacturing 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 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 the adhesive remaining on the separated wafer with a cleaning agent, wherein the cleaning agent is a cleaning agent composition that contains a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and that is water-free or contains 10 mass% or less of water, and has a mass ratio A / B of Component A to Component B of 1.7 or less.

[0041] 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 each step of the method for manufacturing a semiconductor substrate according to the present disclosure. Fig. 2 is a schematic diagram for explaining each step in one embodiment of the method for manufacturing a semiconductor substrate according to the present disclosure.

[0042] <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.

[0043] Examples of the wafer used in step (1) include silicon wafers and glass wafers having a diameter of 100 to 500 mm and a thickness of 500 to 2000 μm.

[0044] 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 500 to 20,000 μm.

[0045] The adhesive used in step (1) is not particularly limited as long as it can bond the wafer to the fixing member, has durability sufficient to withstand the polishing step and the processing step, and allows the wafer 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 polyimide-based, 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.

[0046] 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.

[0047] 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.

[0048] <Process (2): Polishing process> Step (2) is a step (polishing step) of polishing the back surface 3a of the wafer 3 opposite to the adhesive surface to which the fixing member 1 is bonded (the surface opposite to the adhesive surface) (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.

[0049] <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.

[0050] <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.

[0051] <Step (5): Cleaning step> Step (5) is a step (cleaning step) of removing adhesive (adhesive residue) 2a remaining on the separated wafer 3 with a cleaning agent (step S5). The cleaning agent used in step (5) may be the cleaning composition or adhesive remover of the present disclosure described above. The cleaning method (adhesive removal method) in the cleaning step includes, for example, immersion cleaning. The immersion conditions for immersion cleaning are, for example, a cleaning agent temperature of preferably 40°C or higher and 70°C or lower, and an immersion time of preferably 1 minute or higher and 60 minutes or lower. It is preferable that ultrasonic vibrations are applied to the cleaning agent, for example, preferably 25 to 50 kHz, and more preferably 35 to 45 kHz from the viewpoint of suppressing damage to the wafer. After cleaning, the wafer may be rinsed with water or alcohol and then dried.

[0052] [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 the adhesive remaining on the wafer with a cleaning agent after separating the wafer, which has been adhesively bonded to a fixing member from the fixing member, from the fixing member, wherein the cleaning agent is a cleaning agent composition that contains a glycol ether (component A), a hydrocarbon (component B), and an alkanolamine having a linear alkanol group (component C), and that is water-free or contains 10 mass% or less of water, and has a mass ratio A / B of 1.7 or less of the content of component A to the content of component B. In one or more embodiments, the cleaning agent is the cleaning agent composition or adhesive remover of the present disclosure described above. The cleaning method (adhesive removal method) in the cleaning step of the cleaning method of the present disclosure may be the same as the cleaning method (removal method) in step (5) of 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.

[0053] [kit] In one aspect, the present disclosure relates to a kit (hereinafter also referred to as the "kit of the present disclosure") for use in either the cleaning method of the present disclosure or the semiconductor substrate manufacturing method of the present disclosure. In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition or adhesive remover of the present disclosure. The kit of the present disclosure makes it possible to obtain a cleaning composition or adhesive remover that has excellent adhesive removability.

[0054] One embodiment of the kit of the present disclosure is a kit (three-liquid cleaning composition) that contains a solution containing component A (first liquid), a solution containing component B (second liquid), and a solution containing component C (third liquid) in a mutually unmixed state, and the first, second, and third liquids are mixed at the time of use. After the first, second, and third liquids are mixed, they may be diluted with water (component D) as needed. Each of the first, second, and third liquids may contain the optional components described above as needed. Another embodiment of the kit of the present disclosure is a kit (two-liquid cleaning composition) that contains a solution (first liquid) containing components A and B and a solution (second liquid) containing component C in a mutually unmixed state, and the first and second liquids are mixed at the time of use. After the first and second liquids are mixed, they may be diluted with component D (water) as needed. Each of the first and second liquids may contain the optional components described above as needed. [Example]

[0055] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples in any way.

[0056] 1. Preparation of cleaning compositions of Examples 1 to 9 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 9 and Comparative Examples 1 to 5.

[0057] The cleaning compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared using the following materials. (Component A) PGME: 1-methoxy-2-propanol [Fujifilm Wako Pure Chemical Industries, Ltd., special grade] Butyl glycol [Fujifilm Wako Pure Chemical Industries, Ltd., Grade 1] BDG: Butyl diglycol [Nihon Nyukazai Co., Ltd., diethylene glycol monobutyl ether] (Component B) Cyclohexane [Fujifilm Wako Pure Chemical Industries, Ltd., special grade] Ethylbenzene [Fujifilm Wako Pure Chemical Industries, Ltd., special grade] Xylene [Special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] Mesitylene [Fujifilm Wako Pure Chemical Industries, Ltd., special grade] (Component C) Monoethanolamine [Nippon Shokubai Co., Ltd.] (Non-ingredient C) Isopropanolamine: (±)-1-amino-2-propanol [Fujifilm Wako Pure Chemical Industries, Ltd.] (Component D) Water [pure water of 1 μS / cm or less produced using the Organo Corporation G-10DSTSET water purification system]

[0058] 2. Evaluation of the cleaning compositions of Examples 1 to 9 and Comparative Examples 1 to 5 The prepared cleaning compositions of Examples 1 to 9 and Comparative Examples 1 to 5 were evaluated as follows.

[0059] [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 9 and Comparative Examples 1 to 5, and the beaker was heated to 60°C. Test pieces 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 50x magnification using an optical microscope, the "Digital Microscope VHX-2000" (Keyence Corporation). The remaining adhesive was identified in all areas where adhesive was present before cleaning using the brightness extraction function. The area of ​​residual adhesive was calculated using an area calculation tool. The cleaning rate was calculated using the formula below, and the cleaning ability (adhesive removability) was evaluated based on the following criteria. The results are shown in Table 1. Cleaning rate (%) = (adhesive area before cleaning - adhesive area after cleaning) / (adhesive area before cleaning) x 100 <Evaluation criteria> A: Cleaning rate: 99.995% or more B: Cleaning rate: 99.990% or more but less than 99.995% C: Cleaning rate: 99.90% or more but less than 99.990% D: Cleaning rate: less than 99.90% E: Residue observed with the naked eye The test piece was 40 mm x 40 mm in size and consisted of a silicon wafer substrate coated with 5 μm of polybenzoxazole, with adhesive residue present. The adhesive residue was in the form of stripes 50 μm thick and 3 mm wide, spaced 15 mm apart. The adhesive was attached to the test piece and then heat-treated at 290°C for 30 minutes under nitrogen. A methacrylic adhesive was used.

[0060] [Evaluation of Al electrode damage] 100 mL of each of the cleaning compositions of Examples 1 to 9 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 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. 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

[0061] [Table 1]

[0062] As shown in Table 1, the cleaning compositions of Examples 1 to 9 were found to be superior in adhesive removability compared to Comparative Example 1, which did not contain Component B; Comparative Example 2, which did not contain Component C; Comparative Example 3, which used an alkanolamine with a branched carbon chain (non-Component C) as the alkanolamine; Comparative Example 4, which contained more than 10 mass% water and had a mass ratio A / B exceeding 1.7; and Comparative Example 5, which had a mass ratio A / B exceeding 1.7. Comparative Example 5, which had a mass ratio A / B exceeding 1.7, did not exhibit adhesive removability. Furthermore, while Al electrodes can be damaged by polar solvents, the cleaning compositions of Examples 1 to 9 were found to suppress damage to Al electrodes. [Industrial Applicability]

[0063] 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]

[0064] 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 glycol ether (component A), hydrocarbon (component B), and alkanolamine having a linear alkanol group (component C), It contains no water, or the water content is 10% by mass or less. A cleaning agent composition for adhesives, wherein the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

2. The detergent composition according to claim 1, wherein the content of component C is 3% by mass or more and 50% by mass or less.

3. The detergent composition according to claim 1, wherein the number of carbon atoms in component B is 5 or more and 14 or less.

4. The detergent composition according to claim 1, wherein component A contains 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.

5. The detergent composition according to claim 1, wherein component C contains a compound represented by the following formula (II). 【Chemistry 1】 In the above formula (II), R 1 This represents a linear alkanol group with 2 to 4 carbon atoms, and R 2 R represents a linear alkanol group, methyl group, or hydrogen atom having 2 to 4 carbon atoms. 3 This represents a methyl group or a hydrogen atom.

6. The content of component A is 15% by mass or more and 65% by mass or less. The detergent composition according to claim 1, wherein the content of component B is 15% by mass or more and 80% by mass or less.

7. The cleaning agent composition 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. (1) A step of bonding the wafer to the fixing member with an adhesive, (2) A step of polishing the back surface of the bonding surface of the wafer with 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 aforementioned detergent composition contains glycol ether (component A), hydrocarbon (component B), and alkanolamine having a linear alkanol group (component C), contains no water, or has a water content of 10% by mass or less, and has a mass ratio of the content of component A to the content of component B, A / B, of 1.7 or less. A method for manufacturing semiconductor substrates.

9. 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. A cleaning method in which the cleaning agent composition contains glycol ether (component A), hydrocarbon (component B), and alkanolamine having a linear alkanol group (component C), contains no water or has a water content of 10% by mass or less, and the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

10. The cleaning method according to claim 9, wherein the wafer, which is fixed to a fixing member with an adhesive, has been subjected to a heat treatment at a temperature of 230°C or higher.

11. An adhesive remover for removing adhesive residue from a wafer, It contains glycol ether (component A), hydrocarbon (component B), and alkanolamine having a linear alkanol group (component C), It contains no water, or the water content is 10% by mass or less. An adhesive remover in which the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

12. 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. A cleaning method in which the adhesive remover contains glycol ether (component A), hydrocarbon (component B), and alkanolamine having a linear alkanol group (component C), does not contain water, or has a water content of 10% by mass or less, and the mass ratio A / B of the content of component A to the content of component B is 1.7 or less.

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