Method for manufacturing semiconductor substrate

Abstract

The present invention provides, in one embodiment, a method for manufacturing a semiconductor substrate using a cleaning agent composition having excellent adhesive removability. The present invention relates to a method for manufacturing a semiconductor substrate, comprising: (1) a step for bonding a wafer to a fixing member by means of an adhesive; (2) a step for polishing the back surface of the surface of the wafer that is bonded to the fixing member; (3) a step for processing the polished surface of the wafer; (4) a step of separating the processed wafer from the fixing member; and (5) a step for removing the adhesive remaining on the separated wafer with a cleaning agent. The step (3) includes heat-treating the wafer fixed to the fixing member by an adhesive at a temperature of 230 DEG C or higher, and the cleaning agent used in the step (5) is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether (component B) represented by formula (I), the content of the component A being 35-85 mass% (inclusive). And R-O-(EO) n-H (I).

Description

Technical Field

[0001] The present invention relates to a method for producing a semiconductor substrate, a cleaning method, an adhesive cleaning agent composition, and an adhesive remover. Background Art

[0002] In recent years, the high integration of semiconductor components has been developing rapidly, and three-dimensional integrated circuit (3DIC) technology has attracted attention. 3DIC technology is a technology that stacks wafers into multiple layers while connecting them through silicon vias (TSVs) and the like. When stacking wafers into multiple layers, the following processing is required: the back side of the wafer with circuits formed (the side without circuits formed) is ground to make it thinner, and then electrodes are formed on the back side.

[0003] Before thinning, the wafer is bonded (temporarily bonded) to a fixing member (support) using an adhesive, and after processing such as grinding and electrode formation, the wafer is separated from the fixing member. Most of the wafers separated from the fixing member have residual adhesive, and abnormalities sometimes occur in subsequent processes. Therefore, a cleaning process is performed to remove the adhesive remaining on the wafer, and various cleaning agent compositions used in the cleaning process have been developed.

[0004] For example, WO2016 / 021646 (Patent Document 1) discloses a secondary processing solvent (cleaning agent) for cleaning an adhesive layer attached to a semiconductor circuit forming substrate or a supporting substrate after peeling, and the secondary processing solvent contains at least an amine solvent and a specific glycol ether solvent. In addition, the examples of the document disclose a secondary processing solvent containing monoethanolamine, dipropylene glycol dimethyl ether and N-methyl-2-pyrrolidone. Summary of the invention

[0005] The present invention relates in one embodiment to a method for manufacturing a semiconductor substrate, comprising the following steps: (1) a step of bonding a wafer to a fixing member using an adhesive; (2) a step of grinding the back side of the surface of the wafer bonded to the fixing member; (3) a step of processing the ground surface of the wafer; (4) a step of separating the processed wafer from the fixing member; and (5) a step of removing the adhesive remaining on the separated wafer using a cleaning agent; and in the method for manufacturing a semiconductor substrate, the above-mentioned step (3) includes heating the wafer fixed to the fixing member using the adhesive at a temperature of 230° C. or above, and the above-mentioned cleaning agent used in the above-mentioned step (5) is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether (component B) represented by the following formula (I), and the content of component A is 35% by mass or more and 85% by mass or less.

[0006] RO-(EO)nH (I)

[0007] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

[0008] The present invention relates in one embodiment to a cleaning method, comprising the following steps: after a wafer that has been bonded to a fixing member with an adhesive and subjected to a heat treatment at a temperature of 230° C. or higher is separated from the fixing member, the adhesive remaining on the wafer is removed by a cleaning agent; the cleaning agent is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether (component B) represented by the following formula (I), and the content of component A is greater than 35% by mass and less than 85% by mass.

[0009] RO-(EO)nH (I)

[0010] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

[0011] The present invention relates in one embodiment to an adhesive cleaning composition, which is a cleaning composition for removing adhesive remaining on a heat-treated wafer, and contains an alkanolamine (component A) and a glycol ether (component B) represented by the following formula (I), wherein the content of component A is 35 mass % or more and 85 mass % or less.

[0012] RO-(EO)nH (I)

[0013] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

[0014] The present invention relates in one embodiment to an adhesive remover for removing adhesive remaining on a heat-treated wafer, and contains an alkanolamine (component A) and a glycol ether (component B) represented by the following formula (I), wherein the content of component A is 35 mass % or more and 85 mass % or less.

[0015] RO-(EO)nH (I)

[0016] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

[0017] The present invention relates in one embodiment to a cleaning method, which includes the following steps: after a wafer that has been bonded to a fixing component with an adhesive and subjected to a heat treatment at a temperature of 230° C. or above is separated from the fixing component, the adhesive remaining on the wafer is removed using an adhesive remover; the adhesive remover contains an alkanolamine (component A) and a glycol ether (component B) represented by the following formula (I), and the content of component A is greater than 35% by mass and less than 85% by mass.

[0018] RO-(EO)nH (I)

[0019] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a flowchart showing each step of the method for manufacturing a semiconductor substrate of the present invention.

[0021] Figure 2 This is a schematic diagram for explaining each step in one embodiment of the method for manufacturing a semiconductor substrate of the present invention. DETAILED DESCRIPTION

[0022] In the manufacturing process of three-dimensional integrated circuits (3DIC), electrode formation and other processes after grinding of a wafer bonded (temporarily bonded) to a fixing member (support) by an adhesive are sometimes performed at a high temperature of 150°C or higher. If the adhesive is heated and deteriorates, it tends to be difficult to remove. The cleaning agent composition is required to have excellent removability (cleaning properties) for such adhesives.

[0023] The cleaning agent composition proposed in Patent Document 1 has room for improvement in the removal of adhesive remaining on the wafer. In addition, N-methyl-2-pyrrolidone is an organic solvent excellent in terms of high solubility, high boiling point, low freezing point, etc., but from the perspective of safety such as toxicity, it is desired to limit its usage.

[0024] According to the present invention, there can be provided a method for manufacturing and a method for cleaning a semiconductor substrate using an adhesive cleaning composition and an adhesive remover having excellent adhesive removability, and an adhesive cleaning composition and an adhesive remover having excellent adhesive removability.

[0025] Therefore, the present invention provides a method for producing and cleaning a semiconductor substrate using an adhesive cleaning composition and an adhesive remover having excellent adhesive removability, and an adhesive cleaning composition and an adhesive remover having excellent adhesive removability.

[0026] The present invention is based on the finding that adhesive remaining on a wafer subjected to a heat treatment at a temperature of 230° C. or higher can be efficiently removed by using a cleaning composition or adhesive remover containing 35% by mass or more and 85% by mass or less of an alkanolamine and a specific glycol ether.

[0027] The present invention relates in one embodiment to a method for manufacturing a semiconductor substrate (hereinafter also referred to as "the method for manufacturing a semiconductor substrate of the present invention"), which includes the following steps: (1) a step of bonding a wafer to a fixing member using an adhesive; (2) a step of grinding the back side of the surface of the wafer bonded to the fixing member; (3) a step of processing the ground surface of the wafer; (4) a step of separating the processed wafer from the fixing member; and (5) a step of removing the adhesive remaining on the separated wafer using a cleaning agent; wherein the above step (3) includes heating the wafer fixed to the fixing member using the adhesive at a temperature of 230° C. or above, and the above cleaning agent used in the above step (5) is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether (component B) represented by the above formula (I), and the content of component A is 35% by mass or more and 85% by mass or less.

[0028] The present invention, in another embodiment, relates to an adhesive cleaning composition (hereinafter also referred to as "the cleaning composition of the present invention"), which is a cleaning composition for removing adhesive remaining on a heat-treated wafer, and contains an alkanolamine (component A) and a glycol ether (component B) represented by the above formula (I), wherein the content of component A is greater than 35% by mass and less than 85% by mass.

[0029] The present invention, in another embodiment, relates to an adhesive remover (hereinafter also referred to as "the adhesive remover of the present invention"), which is used to remove adhesive remaining on a wafer that has been subjected to a heat treatment, and contains an alkanolamine (component A) and a glycol ether (component B) represented by the above formula (I), wherein the content of component A is greater than 35 mass % and less than 85 mass %.

[0030] According to the present invention, in one or more embodiments, by using a cleaning agent composition with excellent adhesive removal performance, a high-quality semiconductor substrate can be obtained with high yield. According to the present invention, in another one or more embodiments, a cleaning agent composition with excellent adhesive removal performance and an adhesive remover can be provided.

[0031] The details of the mechanism of action of the semiconductor substrate manufacturing method, cleaning composition, and adhesive remover of the present invention for achieving the effects are still unclear, but are presumed as follows.

[0032] The adhesive remaining on the wafer tends to become hard and difficult to remove if it is altered by heating.

[0033] It is believed that in the semiconductor substrate manufacturing method of the present invention, the cleaning agent composition and the adhesive remover of the present invention, a specified amount of alkanolamine (component A) penetrates into the hardened adhesive remaining in the heat-treated wafer and reacts with the reaction points present in the adhesive, thereby reducing the hardness of the adhesive. It is believed that by allowing the glycol ether (component B) with high permeability to act on the adhesive in a state of reduced hardness, the swelling and dissolution of the adhesive are promoted, and the adhesive is removed. It is also believed that when the content of glycol ether (component B) and the mass ratio (A / B) of the content of alkanolamine (component A) relative to the content of glycol ether (component B) are specific values, the permeability of alkanolamine (component A) and glycol ether (component B) is synergistically improved.

[0034] However, the present invention should not be construed as being limited to this mechanism.

[0035] In one or more embodiments, the cleaning composition and adhesive remover of the present invention are used to remove adhesive from a wafer to which adhesive is attached. That is, the present invention relates in one embodiment to a use of the cleaning composition and adhesive remover of the present invention, which is used to remove adhesive from a wafer to which adhesive is attached.

[0036] As the wafer, for example, a semiconductor substrate can be cited. As the semiconductor substrate, for example, a silicon wafer, a germanium wafer, a gallium-arsenic wafer, a gallium-phosphorus wafer, a gallium-arsenic-aluminum wafer, etc. can be cited. In addition, in one or more embodiments, the wafer may also be a substrate having a pad and / or a soldering pad as a portion for bonding and mounting.

[0037] As the adhesive, for example, there can be mentioned an adhesive that can bond the wafer to the fixing member, has durability to withstand the grinding process and the processing process, and can easily separate the wafer from the fixing member in the separation process. As the adhesive, for example, there can be mentioned: polyimide-based, polysiloxane-based, acrylic-based, or methacrylic-based adhesives (adhesive compositions) and the like.

[0038] [Method for manufacturing semiconductor substrate]

[0039] use Figure 1 and Figure 2 The method for producing a semiconductor substrate of the present invention will be described. Figure 1 It is a flowchart showing each step of the method for manufacturing a semiconductor substrate of the present invention. Figure 2 This is a schematic diagram for explaining each step in one embodiment of the method for manufacturing a semiconductor substrate of the present invention.

[0040] <Step (1): Bonding step>

[0041] Step (1) is a step (bonding step) of bonding the wafer 3 to the fixing member 1 using the adhesive 2 (step S1). In one or more embodiments, step (1) includes the following steps: step (1-1) of applying the adhesive to the surface of the wafer or the fixing member to form an adhesive layer; and step (1-2) of bonding the wafer and the fixing member via the adhesive layer and performing a heat treatment to bond them.

[0042] Examples of the wafer used in step (1) include a silicon wafer and a glass wafer having a diameter of 100 to 500 mm and a thickness of 500 to 2000 μm.

[0043] The fixing member used in step (1) is not particularly limited, and 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.

[0044] The adhesive used in step (1) is not particularly limited, as long as the wafer can be bonded to the fixed component, has durability that can withstand the grinding process and the processing process, and can easily separate the wafer from the fixed component in the separation process. For example, the adhesive used in the manufacturing process of 3DIC can be cited. As the adhesive used in the manufacturing process of 3DIC, for example, polyimide-based, polysiloxane-based, acrylic, or methacrylic adhesives (adhesive compositions) can be cited. Specifically, the adhesive composition described in Japanese Patent Gazette No. 2021-161196 can be cited.

[0045] In one or more embodiments, the adhesive composition used in step (1) may include an adhesive composition containing polysiloxane, acrylate, or methacrylate as an adhesive component, or may further contain a platinum group metal catalyst, a release agent component, a solvent, and the like.

[0046] The viscosity of the adhesive composition used in step (1) can be adjusted by appropriately changing the concentration of the components contained in accordance with the coating method, film thickness, and the like.

[0047] In the step (1-1), the method for applying the adhesive (adhesive composition) is not particularly limited, and examples thereof include spin coating.

[0048] Examples of the film thickness of the coating layer (adhesive layer) of the adhesive (adhesive composition) include 5 to 500 μm.

[0049] In the step (1-2), the temperature of the heat treatment is, for example, 80° C. or higher, but is preferably 150° C. or lower from the viewpoint of suppressing excessive curing of the adhesive.

[0050] The time for the heat treatment may be, for example, 30 seconds or longer, but is preferably 10 minutes or shorter from the viewpoint of suppressing the deterioration of the adhesive layer and other members.

[0051] Heating can be performed using a hot plate, an oven, or the like.

[0052] The thickness of the adhesive layer after the heat treatment may be, for example, 5 μm or more and 100 μm or less.

[0053] <Step (2): Grinding step>

[0054] Step (2) is a step of polishing the back surface (surface opposite to the bonding surface) 3a of the wafer 3 bonded to the fixing member 1 (polishing step) (step S2).

[0055] Examples of the polishing method include mechanical polishing using abrasive grains and the like, and chemical mechanical polishing.

[0056] In the step (2), the thickness of the wafer after grinding (thinned wafer) is preferably 200 μm or less, and for example, 50 μm to 200 μm.

[0057] <Process (3): Processing process>

[0058] Step (3) is a step (processing step) of processing the polished surface (the back surface of the thinned wafer) 3a of the wafer 3 (step S3).

[0059] In one or more embodiments, the step (3) may include an electrode forming step, a metal wiring forming step, a protective film forming step, etc. For example, conventionally known processing steps such as metal sputtering, wet etching, resist coating, pattern formation, resist stripping, dry etching, metal plating formation, silicon etching for forming through silicon vias (TSVs), and oxide film formation on the silicon surface for forming electrodes may be included.

[0060] In one or more embodiments, in step (3), the processing is performed at a high temperature of 150°C or higher. In one or more embodiments, the processing includes heating the wafer fixed to the fixing member with an adhesive at a temperature of 230°C or higher. When forming electrodes such as TSV, the processing may include heating at a temperature of 250°C or higher and 350°C or lower.

[0061] <Step (4): Separation step>

[0062] Step (4) is a step of separating the processed wafer 3 from the fixing member 1 (separation step) (step S4).

[0063] Examples of the separation method include solvent peeling, laser peeling, and mechanical peeling.

[0064] <Step (5): Cleaning step>

[0065] Step (5) is a step (cleaning step) of removing the adhesive (adhesive residue) 2a remaining on the separated wafers 3 using a cleaning agent (step S5).

[0066] Examples of the cleaning agent used in step (5) include the cleaning agent composition or adhesive remover of the present invention described later.

[0067] As a cleaning method (adhesive removal method) in the cleaning process, for example, immersion cleaning can be cited. As immersion conditions for immersion cleaning, for example, the temperature of the cleaning agent is preferably 20° C. to 70° C., or 40° C. to 70° C., and the immersion time is preferably 1 minute to 60 minutes. It is preferred to impart ultrasonic vibration 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.

[0068] The cleaned wafer may be washed with water or rinsed with alcohol and then dried.

[0069] [Cleaning agent composition and adhesive remover]

[0070] In one or more embodiments, the cleaning agent composition and the adhesive remover of the present invention are used as a cleaning agent or an adhesive remover for removing an adhesive remaining on a heat-treated wafer.

[0071] <Alkanolamine (ingredient A)>

[0072] The cleaning agent composition and adhesive remover of the present invention contain alkanolamine (amino alcohol) (hereinafter, also referred to as "component A"). As component A, for example, a compound represented by the following formula (II) can be cited. Component A can be one or a combination of two or more. In one or more embodiments, component A is a compound without a branched carbon chain. The content of the compound represented by the following formula (II) in component A is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 100% by mass.

[0073] [Chemical formula 1]

[0074]

[0075] In the above formula (II), R 1 represents a straight-chain alkanol group having 2 or more and 4 or less carbon atoms, R 2 represents a linear alkanol group having 2 to 4 carbon atoms, a methyl group or a hydrogen atom, and R3 represents a methyl group or a hydrogen atom.

[0076] In the above formula (II), from the viewpoint of improving the removability of the adhesive, R 1 Preferably, it is a straight-chain alkanol group having 2 or 3 carbon atoms. 2 Preferably, it is a hydrogen atom. Based on the same viewpoint, R 3 Preferred is a hydrogen atom.

[0077] As component A, for example, 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 can be cited. Among these, from the viewpoint of improving the removability of the adhesive, alkylmonoalkanolamine or monoalkanolamine is preferred, and monoethanolamine is more preferred.

[0078] From the viewpoint of improving the removability of the adhesive, the content of component A in the cleaning composition and adhesive remover of the present invention is 35% by mass or more, preferably 37.5% by mass or more, and more preferably 40% by mass or more, and from the viewpoint of improving the removability of the adhesive, reducing component damage, and nitrogen content, it is 85% by mass or less, preferably 75% by mass or less, and more preferably 65% ​​by mass or less. More specifically, the content of component A in the cleaning composition and adhesive remover of the present invention is 35% by mass or more and 85% by mass or less, preferably 37.5% by mass or more and 75% by mass or less, and more preferably 40% by mass or more and 65% by mass or less. In the case where component A is a combination of two or more, the content of component A refers to their total content.

[0079] In the present invention, “the content of each component in the cleaning composition and the adhesive remover” may refer to the content of each component at the time of cleaning, that is, when the cleaning composition and the adhesive remover are started to be used for cleaning.

[0080] In one or more embodiments, the content of each component in the cleaning composition and the adhesive remover of the present invention can be regarded as the blending amount of each component in the cleaning composition and the adhesive remover of the present invention.

[0081] <Glycol ether (component B)>

[0082] The cleaning composition and adhesive remover of the present invention contain a glycol ether represented by the following formula (I) (hereinafter also referred to as "component B"). Component B may be one kind or a combination of two or more kinds.

[0083] RO-(EO)nH (I)

[0084] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

[0085] As component B, from the viewpoint of improving the removability of the adhesive, preferably, it is a (poly)ethylene glycol monoalkyl ether having an alkyl group with a carbon number of 1 to 4, more preferably at least one selected from ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group with a carbon number of 1 to 4, and further preferably at least one selected from ethylene glycol monobutyl ether (BG) and diethylene glycol monobutyl ether (BDG).

[0086] From the viewpoint of improving the removability and compatibility of the adhesive, the content of component B in the cleaning composition and adhesive remover of the present invention is preferably 15% by mass or more, more preferably 30% by mass or more, and more preferably 45% by mass or more, and from the viewpoint of improving the removability of the adhesive, preferably 65% ​​by mass or less, more preferably 62.5% by mass or less, and more preferably 60% by mass or less. More specifically, the content of component A in the cleaning composition and adhesive remover of the present invention is preferably 15% by mass or more and 65% by mass or less, more preferably 30% by mass or more and 62.5% by mass or less, and more preferably 45% by mass or more and 60% by mass or less. In the case where component B is a combination of two or more, the content of component B refers to their total content.

[0087] From the viewpoint of cleaning properties and stability, the mass ratio A / B of the content of component A to the content of component B is preferably 0.6 or more, more preferably 0.625 or more, and further preferably 0.65 or more, and from the viewpoint of cleaning properties and stability, it is preferably 5.5 or less, more preferably 3 or less, and further preferably less than 1. More specifically, the mass ratio A / B is preferably 0.6 or more and 5.5 or less, more preferably 0.625 or more and 3 or less, and further preferably 0.65 or more and less than 1.

[0088] <Water (ingredient C)>

[0089] The cleaning agent composition and adhesive remover of the present invention preferably do not contain water, or the water content is 15% by mass or less. In one or more embodiments, water (hereinafter also referred to as "component C") may include: ion exchange water, RO (Reverses Osmosis) water, distilled water, pure water, ultrapure water, etc.

[0090] When the cleaning composition and adhesive remover of the present invention contain component C, the content of component C in the cleaning composition and adhesive remover of the present invention may be the remaining content excluding component A, component B, and optional components described later. Specifically, from the viewpoint of improving the removability of the adhesive, the content of component C in the cleaning composition and adhesive remover of the present invention is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less, and further preferably substantially 0% by mass (i.e., not containing).

[0091] <Other ingredients>

[0092] The cleaning agent composition and adhesive remover of the present invention may further contain water (component C) or other components as required in addition to the above-mentioned components A to B. As other components, components that can be used in common cleaning agents can be cited, for example, solvents other than component C, alkaline agents other than component A, amines other than component A, surfactants, chelating agents, thickeners, dispersants, rust inhibitors, polymer compounds, solubilizers, antioxidants, preservatives, defoaming agents, antibacterial agents, etc. can be cited.

[0093] The cleaning composition and adhesive remover of the present invention preferably contain no N-methyl-2-pyrrolidone, or contain 1% by mass or less of N-methyl-2-pyrrolidone.

[0094] When the cleaning composition of the present invention contains N-methyl-2-pyrrolidone, the content of N-methyl-2-pyrrolidone in the cleaning composition and adhesive remover of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, further preferably 0.01% by mass or less, and still further preferably essentially 0% by mass (i.e., containing no N-methyl-2-pyrrolidone) from the viewpoint of safety such as toxicity and compliance with various regulations.

[0095] In one or more embodiments, the cleaning composition and adhesive remover of the present invention 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 invention is preferably less than 1% by mass, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and further preferably 0% by mass.

[0096] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may be substantially free of nonionic surfactants. For example, the content of nonionic surfactants in the cleaning composition and adhesive remover of the present invention is preferably less than 1% by mass, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and further preferably 0% by mass. Examples of nonionic surfactants include products obtained by adding any ethylene oxide or propylene oxide to an aliphatic hydrocarbon or aromatic hydrocarbon having 8 to 10 carbon atoms.

[0097] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may contain substantially no aliphatic hydrocarbons having carbon numbers of 9 to 16. For example, the content of aliphatic hydrocarbons having carbon numbers of 9 to 16 in the cleaning composition and adhesive remover of the present invention 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.

[0098] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may be substantially free of hydroxylamine. For example, the content of hydroxylamine in the cleaning composition and adhesive remover of the present invention is preferably less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and more preferably 0% by mass.

[0099] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may be substantially free of glyoxylic acid. For example, the content of glyoxylic acid in the cleaning composition and adhesive remover of the present invention is preferably less than 0.05% by mass, preferably less than 0.01% by mass, and more preferably 0% by mass.

[0100] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may be substantially free of N,N-dimethylacetamide (DMAC). For example, the content of N,N-dimethylacetamide (DMAC) in the cleaning composition and adhesive remover of the present invention is preferably less than 0.1% by mass, preferably 0.01% by mass or less, and more preferably 0% by mass.

[0101] In one or more embodiments, the cleaning composition and adhesive remover of the present invention may be substantially free of quaternary ammonium hydroxide. For example, the content of quaternary ammonium hydroxide in the cleaning composition and adhesive remover of the present invention is preferably less than 1% by mass, preferably less than 0.1% by mass, and more preferably 0% by mass.

[0102] [Cleaning agent composition and method for producing adhesive remover]

[0103] In one or more embodiments, the cleaning composition and adhesive remover of the present invention can be manufactured by combining the above-mentioned components A to B and the above-mentioned optional components (component C, other components) as required using a known method. For example, the cleaning composition and adhesive remover of the present invention can be formed by combining at least the above-mentioned components A to B. Therefore, the present invention relates to a method for manufacturing a cleaning composition and an adhesive remover comprising a step of combining at least the above-mentioned components A to B. In the present invention, "combination" includes mixing components A to B and the above-mentioned optional components (component C, other components) as required simultaneously or in any order. In the method for manufacturing the cleaning composition and adhesive remover of the present invention, the preferred amount of each component may be the same as the preferred content of each component of the cleaning composition and adhesive remover of the present invention described above.

[0104] [Object to be cleaned]

[0105] As the object to be cleaned, for example, a wafer with an adhesive attached thereto can be cited. As the wafer, for example, a semiconductor substrate can be cited. As the semiconductor substrate, for example, wafers such as silicon wafers, germanium wafers, gallium-arsenic wafers, gallium-phosphorus wafers, and gallium-arsenic-aluminum wafers can be cited. In addition, in one or more embodiments, as the wafer, it can also be a substrate having pads and / or solder pads as a portion for bonding and mounting. As components of the pads and solder pads, for example, metals such as gold or copper can be cited.

[0106] In one or more embodiments, as a wafer with an adhesive attached, examples include: a wafer after a wafer bonded (fixed) to a fixing member with an adhesive is separated from the fixing member, a wafer bonded (fixed) to a fixing member with an adhesive and subjected to a heat treatment under a temperature condition of 230°C or above is separated from the fixing member, etc. Therefore, the present invention relates in one embodiment to a use of a cleaning agent composition or an adhesive remover of the present invention, which is used as a cleaning agent for removing the adhesive remaining on the wafer after a wafer bonded (fixed) to a fixing member with an adhesive is separated from the fixing member. In one or more embodiments, a wafer bonded (fixed) to a fixing member with an adhesive has been subjected to a heat treatment under a temperature condition of 230°C or above. In one or more embodiments, as the above-mentioned heat treatment, a heat treatment in a processing step described later can be cited.

[0107] In one or more embodiments, the wafer to which the adhesive is attached may be a wafer to which the adhesive used in the manufacturing process of a three-dimensional integrated circuit (3DIC) is attached. Therefore, the present invention relates in one embodiment to the use of a cleaning agent composition or adhesive remover of the present invention as a cleaning agent for removing an adhesive used in the manufacturing process of a three-dimensional integrated circuit.

[0108] In one or more embodiments, the wafer with the adhesive attached thereto is 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 a processing step described later.

[0109] [Cleaning method]

[0110] The present invention relates in one embodiment to a cleaning method (hereinafter also referred to as "the cleaning method of the present invention"), which includes the following steps: after a wafer that has been bonded to a fixing member with an adhesive and has been subjected to a heat treatment at a temperature of 230°C or higher is separated from the fixing member, a step (cleaning step) of removing the adhesive remaining on the wafer with a cleaning agent; the cleaning agent is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether (component B) represented by the above formula (I), and the content of component A is 35% by mass or more and 85% by mass or less. In one or more embodiments, the cleaning agent is the cleaning agent composition or adhesive remover of the present invention.

[0111] Examples of the cleaning method (adhesive removal method) in the cleaning step of the cleaning method of the present invention include the same methods as the cleaning method (removal method) in step (5) in the semiconductor substrate manufacturing method of the present invention.

[0112] In one or more embodiments, in the cleaning method of the present invention, the wafer that is bonded to the fixing member by an adhesive and subjected to a heat treatment at a temperature of 230° C. or higher is preferably a wafer that is subjected to a heat treatment at a temperature of 270° C. or higher. As a heat treatment at a temperature of 230° C. or higher, for example, a heat treatment for joining components such as semiconductor chips and substrates formed with other circuits to a substrate formed with a circuit using solder or metal particles can be cited. As a heat treatment process, it can be cited that it is performed after the processing process of process (3) and before process (4).

[0113] In one or more embodiments, the object to be cleaned in the cleaning method of the present invention may be a wafer that has been through steps (1) to (4) in the method for manufacturing a semiconductor substrate of the present invention.

[0114] [Set]

[0115] The present invention relates in one embodiment to a kit (hereinafter also referred to as "the kit of the present invention"), which is used in any one of the cleaning method of the present invention and the semiconductor substrate manufacturing method of the present invention. In one or more embodiments, the kit of the present invention is used to manufacture the cleaning composition or adhesive remover of the present invention. According to the kit of the present invention, a cleaning composition or adhesive remover having excellent adhesive removal properties can be obtained.

[0116] In one or more embodiments, as a kit of the present invention, there can be cited a kit (two-liquid cleaning composition) that contains a solution containing component A (first liquid) and a solution containing component B (second liquid) in an unmixed state, and the first liquid and the second liquid are mixed when used. After the first liquid and the second liquid are mixed, they can also be diluted with water (component C) as needed. The first liquid and the second liquid can each contain the above-mentioned optional components as needed.

[0117] Example

[0118] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples at all.

[0119] 1. Preparation of cleaning agent compositions of Examples 1 to 3 and Comparative Example 1

[0120] The components shown in Table 1 were blended in the amounts (mass %, active ingredient) shown in Table 1, and stirred and mixed to prepare cleaning compositions of Examples 1 to 3 and Comparative Example 1.

[0121] The cleaning compositions of Examples 1 to 3 and Comparative Example 1 were prepared using the following components.

[0122] (ingredient A)

[0123] Monoethanolamine [manufactured by Nippon Catalyst Co., Ltd.]

[0124] (ingredient B)

[0125] BDG: Diethylene glycol butyl ether [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether]

[0126] BG: Ethylene glycol butyl ether [manufactured by Nippon Emulsifier Co., Ltd., ethylene glycol monobutyl ether]

[0127] (Non-ingredient B)

[0128] Dipropylene glycol dimethyl ether [manufactured by Nippon Emulsifier Co., Ltd.]

[0129] (Ingredient C)

[0130] Water [pure water with a concentration of 1 μS / cm or less produced by the pure water device G-10DSTSET manufactured by Organo Co., Ltd.]

[0131] 2. Evaluation of the cleaning compositions of Examples 1 to 3 and Comparative Example 1

[0132] The cleaning compositions of Examples 1 to 3 and Comparative Example 1 thus prepared were evaluated as follows.

[0133] [Evaluation of cleaning properties (adhesive removability)]

[0134] 200 mL of the cleaning composition of Examples 1 to 3 and Comparative Example 1 was added to a 200 mL beaker, and the test piece was immersed in the cleaning composition at room temperature (25°C) for 10 minutes. Then, the test piece was taken out from the cleaning composition, and PGME: 1-methoxy-2-propanol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] and ethylene glycol monobutyl ether [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first grade] were flowed for about 20 seconds at room temperature for rinsing, and then left to stand and dry at room temperature.

[0135] The test piece was visually observed for the presence or absence of residual adhesive, the cleaning rate was calculated, and the cleaning property (adhesive removability) was evaluated based on the following evaluation criteria.

[0136] Cleaning rate (%) = (area from which adhesive is removed after cleaning) / (area of ​​test piece) × 100

[0137] <Evaluation Criteria>

[0138] A: No residue is found or the residue area is less than 1% under visual observation.

[0139] B: Under visual observation, the residue area is more than 1% and less than 25%

[0140] C: Under visual observation, the residue area is more than 25% and less than 40%

[0141] D: Under visual observation, the residue area is more than 40% and less than 50%

[0142] E: Under visual observation, the residue area is more than 50%

[0143] It should be noted that the size of the test piece was 30 mm × 30 mm, and the silicon wafer had adhesive residue. The adhesive residue was present on the entire surface of the test piece with a thickness of 20 μm. In addition, the adhesive used was an adhesive that had been heat-treated for 60 minutes under nitrogen and 250°C after being attached to the test piece. The adhesive used was a polyimide-based adhesive.

[0144] [Evaluation of Al electrode damage]

[0145] 100 mL of the cleaning composition of Examples 1 to 3 and Comparative Example 1 was added to a 100 mL beaker and heated to 60°C. The test piece was immersed in the cleaning composition at 60°C for 30 minutes while irradiating ultrasonic waves (40 kHz, 360 W) using an ultrasonic cleaner (ASU-20M, manufactured by Azovon Co., Ltd.). Then, the test piece was taken out from the cleaning composition, rinsed by passing ethanol (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) for about 20 seconds at room temperature, and then left to dry at room temperature.

[0146] The test piece after the cleaning test was magnified 100 times using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE Corporation) and visually checked, and the damage of the Al electrode was evaluated according to the following evaluation criteria.

[0147] It should be noted that the size of the test piece was 15 mm×15 mm, and the silicon wafer had an Al electrode with a size of 3 mm×2.5 mm without any gap.

[0148] <Evaluation Criteria>

[0149] A: No electrode discoloration

[0150] B: Although the electrode does not change color, the gloss is slightly reduced

[0151] C: Although the electrode does not change color, the gloss is reduced

[0152] D: The electrode is found to be discolored

[0153] [Table 1]

[0154]

[0155] As shown in Table 1, it can be seen that the cleaning compositions of Examples 1 to 3 are more excellent in adhesive removal than Comparative Example 1 which does not contain Component B. In addition, it can be seen that although the Al electrode is sometimes damaged by the polar solvent, the cleaning compositions of Examples 1 to 3 can suppress damage to the Al electrode. Furthermore, since the cleaning compositions of Examples 1 to 3 do not contain N-methyl-2-pyrrolidone, they can be considered to be highly safe cleaning compositions.

[0156] Industrial Applicability

[0157] According to the present invention, a cleaning composition having excellent adhesive removal performance can be provided. In addition, by using the cleaning composition of the present invention, the productivity of semiconductor substrates can be improved.

[0158] Description of Reference Numerals

[0159] 1:Fixed components;

[0160] 2: Adhesive;

[0161] 2a: adhesive residue;

[0162] 3: Wafer;

[0163] 3a: Grinding / processing side of the wafer.

Claims

1. A method for manufacturing a semiconductor substrate, comprising the following steps: (1) A step of bonding the wafer to a fixing member using an adhesive; (2) a step of grinding the back side of the surface of the wafer bonded to the fixing member; (3) a step of processing the polished surface of the wafer; (4) a step of separating the processed wafer from the fixing member; and (5) a step of removing the adhesive remaining on the separated wafers using a cleaning agent, The step (3) includes heating the wafer fixed to the fixing member by an adhesive at a temperature of 230° C. or higher. The cleaning agent used in the step (5) is a cleaning agent composition containing component A and component B, wherein the content of component A is 35 mass % or more and 85 mass % or less, component A is an alkanolamine, and component B is a glycol ether represented by the following formula (I): RO-(EO)nH (I) In the formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

2. A cleaning method comprising the steps of: after a wafer that has been bonded to a fixing member with an adhesive and has been subjected to a heat treatment at a temperature of 230° C. or higher is separated from the fixing member, removing the adhesive remaining on the wafer with a cleaning agent; The cleaning agent is a cleaning agent composition containing component A and component B, wherein the content of component A is 35 mass % or more and 85 mass % or less, component A is an alkanolamine, and component B is a glycol ether represented by the following formula (I). RO-(EO)nH (I) In the formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

3. An adhesive cleaning composition, which is a cleaning composition for removing adhesive remaining on a heat-treated wafer, and The invention comprises a component A and a component B, wherein the component A is an alkanolamine and the component B is a glycol ether represented by the following formula (I). The content of component A is 35 mass % or more and 85 mass % or less, RO-(EO)nH (I) In the formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3. 4 . The cleaning composition according to claim 3 , which contains no water or contains water in an amount of 15% by mass or less.

5. The cleaning composition according to claim 3 or 4, wherein The content of Component B is 15% by mass or more and 65% by mass or less.

6. The cleaning composition according to any one of claims 3 to 5, wherein Component A comprises a compound represented by the following formula (II): In the formula (II), R 1 represents a straight-chain alkanol group having 2 or more and 4 or less carbon atoms, R 2 represents a linear alkanol group having 2 to 4 carbon atoms, a methyl group or a hydrogen atom, and R 3 represents a methyl group or a hydrogen atom.

7. The cleaning composition according to any one of claims 3 to 6, wherein The mass ratio A / B of the content of component A to the content of component B is 0.6 or more and 5.5 or less.

8. The cleaning composition according to any one of claims 3 to 7, wherein The adhesive is an adhesive used in the manufacturing process of a three-dimensional integrated circuit.

9. An adhesive remover for removing adhesive remaining on a wafer subjected to a heating treatment, and The invention comprises a component A and a component B, wherein the component A is an alkanolamine and the component B is a glycol ether represented by the following formula (I). The content of component A is 35 mass % or more and 85 mass % or less, RO-(EO)nH (I) In the formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

10. A cleaning method comprising the steps of: removing the adhesive remaining on the wafer with an adhesive remover after a wafer that has been bonded to a fixing member with an adhesive and subjected to a heat treatment at a temperature of 230° C. or higher is separated from the fixing member; The adhesive remover contains component A and component B, wherein the content of component A is 35 mass % or more and 85 mass % or less, component A is an alkanolamine, and component B is a glycol ether represented by the following formula (I). RO-(EO)nH (I) In the formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n represents the number of added moles of EO and is a number of 1 to 3.

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