Manufacturing method for semiconductor substrate
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2023-06-14
- Publication Date
- 2026-04-10
AI Technical Summary
Existing cleaning compositions struggle with effective removability of adhesives on semiconductor wafers after high-temperature processing, and N-methyl-2-pyrrolidone, despite its solubility benefits, raises safety concerns due to toxicity.
A cleaning composition comprising alkanolamine and glycol ether, with specific mass ratios, is used to remove adhesive residues on wafers that have undergone high-temperature processing, enhancing adhesive removability and safety.
The composition effectively removes adhesive residues on semiconductor wafers, improving yield and safety by using alkanolamine and glycol ether, while minimizing damage to the wafers.
Smart Images
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Abstract
Description
Technical Field
[0001] The present disclosure relates to a method for manufacturing a semiconductor substrate, a cleaning method, a cleaning agent composition for an adhesive, and an adhesive remover.
Background Art
[0002] In recent years, the high integration of semiconductor devices has advanced rapidly, and three-dimensional integrated circuit (3DIC) technology has attracted attention. The 3DIC technology is a technology for laminating wafers in multiple layers while connecting the wafers with through-silicon vias (TSVs) or the like. When laminating wafers in multiple layers, it is necessary to perform processes such as thinning the back surface (the surface where no circuit is formed) of the wafer on which the circuit is formed by polishing, and further forming electrodes on the back surface. Before thinning, the wafer is adhesively bonded (temporarily bonded) to a fixing member (support) with an adhesive. After undergoing processes such as polishing and electrode formation, the wafer is separated from the fixing member. Often, the adhesive remains on the wafer separated from the fixing member, which may cause problems in subsequent processes. Therefore, a cleaning process for removing the adhesive remaining on the wafer is performed, and various cleaning agent compositions used 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 formation substrate or a support substrate, which contains at least an amine-based solvent and a specific glycol ether-based solvent. And in the examples, a rework solvent composed of monoethanolamine, dipropylene glycol dimethyl ether, and N-methyl-2-pyrrolidone is disclosed.
Prior Art Documents
Patent Documents
[0004]
Patent Document 1
Summary of the Invention
Problems to be Solved by the Invention
[0005] In the manufacturing process of three-dimensional integrated circuits (3DICs), processing such as electrode formation after polishing wafers that have been temporarily bonded (temporarily bonded) to a fixed member (support) with adhesive may be carried out at high temperatures of 150°C or higher. When the adhesive deteriorates due to heating, it tends to be difficult to remove. Cleaning agent compositions are required to have excellent adhesive removal properties (cleaning properties) in such cases. The cleaning agent composition proposed in Patent Document 1 had room for improvement in its ability to remove adhesive residue from wafers. Furthermore, while N-methyl-2-pyrrolidone is an excellent organic solvent with high solubility, a high boiling point, and a low freezing point, it is desirable to limit its usage from a safety standpoint, such as from the perspective of toxicity.
[0006] Therefore, this disclosure provides an adhesive cleaning agent composition and an adhesive remover that exhibit excellent adhesive removal properties, a method for manufacturing and cleaning a semiconductor substrate using the adhesive remover, and an adhesive cleaning agent composition and adhesive remover that exhibit excellent adhesive removal properties. [Means for solving the problem]
[0007] This disclosure relates to a method for manufacturing a semiconductor substrate, comprising, in one embodiment, the steps of (1) bonding a wafer to a fixing member with an adhesive, (2) polishing the back surface of the bonding surface of the wafer 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 step (3) includes heat-treating the wafer fixed to the fixing member with adhesive at a temperature of 230°C or higher, and the cleaning agent used in step (5) is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), with the content of component A being 35% by mass or more and 85% by mass or less. RO-(EO)nH (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3.
[0008] This disclosure relates to a cleaning method, in one embodiment, which includes the step of separating a wafer that has been bonded to a fixed member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher from the fixed member, and then removing the adhesive remaining on the wafer with a cleaning agent, wherein the cleaning agent is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)nH (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3.
[0009] This disclosure relates, in one embodiment, to a cleaning agent composition for removing adhesive residue from a heat-treated wafer, comprising an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), wherein the content of component A is 35% by mass or more and 85% by mass or less, to an adhesive cleaning agent composition. RO-(EO)nH (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3.
[0010] This disclosure relates, in one embodiment, to an adhesive remover for removing adhesive remaining on a heat-treated wafer, comprising an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), wherein the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)nH (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3.
[0011] This disclosure relates to a cleaning method, in one embodiment, which includes the step of separating a wafer that has been bonded to a fixed member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher from the fixed member, and then removing the adhesive remaining on the wafer with an adhesive remover, wherein the adhesive remover contains an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)nH (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3. [Effects of the Invention]
[0012] According to this disclosure, it is possible to provide an adhesive cleaning agent composition and an adhesive remover that have excellent adhesive removal properties, a method for manufacturing and cleaning a semiconductor substrate using the adhesive remover, and an adhesive cleaning agent composition and adhesive remover that have excellent adhesive removal properties. [Brief explanation of the drawing]
[0013] [Figure 1] Figure 1 is a flowchart showing the steps of the semiconductor substrate manufacturing method according to this disclosure. [Figure 2] Figure 2 is a schematic diagram illustrating each step in one embodiment of the semiconductor substrate manufacturing method of the present disclosure. [Modes for carrying out the invention]
[0014] This disclosure is based on the finding that adhesives remaining on wafers that have been heat-treated at temperatures of 230°C or higher can be efficiently removed by using a cleaning agent composition or adhesive remover containing an alkanolamine in an amount of 35% to 85% by mass and a specific glycol ether.
[0015] In one aspect, the present disclosure relates to a method for manufacturing a semiconductor substrate, comprising: (1) a step of bonding a wafer to a 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 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 wafer with a cleaning agent. The step (3) includes heat-treating the wafer fixed to the fixing member with the adhesive at a temperature of 230 °C or higher. The cleaning agent used in the step (5) is a cleaning agent composition containing alkanolamine (component A) and the glycol ether represented by the above formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less (hereinafter, also referred to as "the method for manufacturing a semiconductor substrate of the present disclosure"). In other aspects, the present disclosure relates to a cleaning agent composition for removing an adhesive remaining on a heat-treated wafer, containing alkanolamine (component A) and the glycol ether represented by the above formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less (hereinafter, also referred to as "the cleaning agent composition of the present disclosure"). In other aspects, the present disclosure relates to an adhesive remover for removing an adhesive remaining on a heat-treated wafer, containing alkanolamine (component A) and the glycol ether represented by the above formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less (hereinafter, also referred to as "the adhesive remover of the present disclosure").
[0016] According to the present disclosure, in one or more embodiments, by using a cleaning agent composition excellent in adhesive removability, a high-quality semiconductor substrate can be obtained with a high yield. According to the present disclosure, in one or more other embodiments, a cleaning agent composition and an adhesive remover excellent in adhesive removability can be provided.
[0017] Although the details of the mechanism of action for the effects of the method for manufacturing a semiconductor substrate, the cleaning agent composition, and the adhesive remover of the present disclosure are unclear in some parts, they are presumed as follows. Adhesives remaining on wafers tend to harden and become difficult to remove once they are altered by heating. In the semiconductor substrate manufacturing method, cleaning agent composition, and adhesive remover disclosed herein, it is believed that a predetermined amount of alkanolamine (component A) penetrates into the hardened adhesive remaining on the heat-treated wafer and reacts with reaction sites present in the adhesive, thereby reducing the adhesive's hardness. It is believed that the highly penetrating glycol ether (component B) acts on the reduced-hardness adhesive, causing swelling and dissolution of the adhesive, and thus removing the adhesive. Furthermore, it is believed that when the content of glycol ether (component B) and the mass ratio of the content of alkanolamine (component A) to the content of glycol ether (component B) (A / B) are specific values, the penetrating power of alkanolamine (component A) and glycol ether (component B) is synergistically increased. However, this disclosure does not have to be interpreted as being limited to this mechanism.
[0018] The cleaning compositions and adhesive removers of the present disclosure are used in one or more embodiments to remove adhesive from wafers to which adhesive has adhered. That is, the present disclosure relates in one embodiment to the use of the cleaning compositions and adhesive removers of the present disclosure for removing adhesive from wafers to which adhesive has adhered. Examples of wafers include semiconductor substrates. Examples of semiconductor substrates include silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. In one or more embodiments, the wafer may also be a substrate having pads and / or lands, which are areas for bonding and mounting. Examples of adhesives include those that can bond wafers to a fixing member, have durability to withstand polishing and processing steps, and allow for easy separation of the wafers from the fixing member during the separation process. Examples of adhesives include polyimide-based, polysiloxane-based, acrylic-based, or methacrylic-based adhesives (adhesive compositions).
[0019] [Manufacturing method for semiconductor substrates] The semiconductor substrate manufacturing method of this disclosure will be described with reference to Figures 1 and 2. Figure 1 is a flowchart of each step in the semiconductor substrate manufacturing method of this disclosure. Figure 2 is a schematic diagram illustrating each step in one embodiment of the semiconductor substrate manufacturing method of this disclosure.
[0020] <Process (1): Adhesion process> Step (1) is a step of bonding the wafer 3 to the fixing member 1 with adhesive 2 (bonding step) (step S1). Step (1) includes, in one or more embodiments, a step of applying adhesive to the surface of the wafer or fixing member to form an adhesive layer (1-1), and a step of bonding the wafer and the fixing member together via the adhesive layer and joining them by heat treatment (1-2).
[0021] Examples of wafers used in process (1) include silicon wafers and glass wafers with a diameter of 100 to 500 mm and a thickness of 500 to 2000 μm.
[0022] The fixing member used in process (1) is not particularly limited, but examples include a silicon wafer or glass plate with a diameter of 100 to 500 mm and a thickness of 500 to 20,000 μm.
[0023] The adhesive used in step (1) is not particularly limited as long as it can bond the wafer to the fixing member, has sufficient durability to withstand the polishing and processing steps, and allows the wafer to be easily separated from the fixing member in the separation step. 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 composition described in Japanese Patent Application Publication No. 2021-161196. The adhesive composition used in step (1) may, in one or more embodiments, include a polysiloxane, an acrylic acid ester, or a methacrylic acid ester as an adhesive component, and may further include 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 depending on the application method, film thickness, etc.
[0024] In step (1-1), the method of applying the adhesive (adhesive composition) is not particularly limited, but examples include the spin coating method. The film thickness of the adhesive coating layer (adhesive layer) of the adhesive (adhesive composition) can be, for example, 5 to 500 μm.
[0025] In step (1-2), the heat treatment temperature can be, for example, 80°C or higher, and is preferably 150°C or lower from the viewpoint of suppressing excessive hardening of the adhesive. The heating time can be, for example, 30 seconds or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is preferable to be 10 minutes or less. Heating can be done using a hot plate, oven, etc. Examples of the thickness of the adhesive layer after heat treatment include 5 μm to 100 μm.
[0026] <Process (2): Polishing process> Step (2) is a polishing step (step S2) in which the back surface (the surface opposite to the adhesive surface) 3a of the wafer 3 that is bonded to the fixing member 1 is polished. Polishing methods include, for example, 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.
[0027] <Process (3): Processing process> Step (3) is a process (processing step) for processing the polished surface (back surface of the thinned wafer) 3a of the wafer 3 (step S3). Step (3) may include, in one or more embodiments, an electrode formation step, a metal wiring formation step, a protective film formation step, etc. Examples of conventionally known processing steps include metal sputtering for electrode formation, wet etching, resist coating, pattern formation, resist stripping, dry etching, metal plating formation, silicon etching for silicon through-silicon (TSV) formation, and oxide film formation on the silicon surface. In step (3), the processing is carried out at a high temperature of 150°C or higher in one or more embodiments. In one or more embodiments, the processing includes heat treatment of a wafer fixed to a fixing member with adhesive at a temperature of 230°C or higher. When forming electrodes such as TSVs, the processing may be heat treatment at a temperature of 250°C to 350°C, for example.
[0028] <Step (4): Separation step> Step (4) is a process (separation step) for separating the processed wafer 3 and the fixing member 1 (step S4). Examples of separation methods include solvent stripping, laser stripping, and mechanical stripping.
[0029] <Process (5): Washing Process> Step (5) is a cleaning step (step S5) in which the adhesive (adhesive residue) 2a remaining on the separated wafer 3 is removed with a cleaning agent. Examples of cleaning agents used in step (5) include the cleaning agent compositions or adhesive removers of this disclosure described later. As a cleaning method (method for removing adhesive) in the cleaning process, for example, immersion cleaning can be used. As for the 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 preferable that ultrasonic vibration is applied to the cleaning agent, for example, 25 to 50 kHz is preferred, and 35 to 45 kHz is more preferable from the viewpoint of suppressing damage to the wafer. After cleaning, the wafers may be rinsed with water or alcohol and then dried.
[0030] [Cleaning agent composition and adhesive remover] The cleaning agent compositions and adhesive removers of this disclosure are used in one or more embodiments as cleaning agents or adhesive removers for removing adhesives remaining on a heat-treated wafer.
[0031] <Alkanolamine (Component A)> The cleaning agent composition and adhesive remover of this disclosure contain an alkanolamine (amino alcohol) (hereinafter also referred to as "component A"). Component A may include, for example, a compound represented by the following formula (II). Component A may be one type or a combination of two or more types. In one or more embodiments, component A is a compound that does not have 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 even more preferably 100% by mass. [ka]
[0032] In the above equation (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. In the above equation (II), R 1 From the viewpoint of improving the removeability of the adhesive, a linear alkanol group having 2 or 3 carbon atoms is preferred. 2 From a similar viewpoint, a hydrogen atom is preferred. 3 From a similar viewpoint, hydrogen atoms are preferred.
[0033] Component A can be, 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. Among these, alkylmonoalkanolamine or monoalkanolamine is preferred from the viewpoint of improving the removeability of the adhesive, and monoethanolamine is more preferred.
[0034] The content of component A in the cleaning agent composition and adhesive remover of this disclosure is preferably 35% by mass or more, more preferably 37.5% by mass or more, and more preferably 40% by mass or more, from the viewpoint of improving adhesive removeability, preventing material damage, and reducing nitrogen content. More specifically, the content of component A in the cleaning agent composition and adhesive remover of this disclosure is preferably 35% by mass or more and 85% by mass or less, more 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. When component A is a combination of two or more types, the content of component A refers to the total content of those types.
[0035] In this disclosure, "content of each component in the cleaning agent composition and adhesive remover" may refer to the content of each component at the time of cleaning, that is, at the time when the cleaning agent composition and adhesive remover are first used for cleaning. The content of each component in the cleaning agent composition and adhesive remover of this disclosure can be considered, in one or more embodiments, as the amount of each component blended in the cleaning agent composition and adhesive remover of this disclosure.
[0036] <Glycol ether (component B)> The cleaning agent composition and adhesive remover of this disclosure contain a glycol ether represented by the following formula (I) (hereinafter also referred to as "component B"). Component B may be one type or a combination of two or more types. RO-(EO)nH (I)
[0037] In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethylene oxy group, and n is the number of moles of EO added, which is between 1 and 3.
[0038] As for component B, from the viewpoint of improving the removeability of the adhesive, a (poly)ethylene glycol monoalkyl ether having an alkyl group with 1 to 4 carbon atoms is preferred, at least one selected from ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether having an alkyl group with 1 to 4 carbon atoms is more preferred, and at least one selected from ethylene glycol monobutyl ether (BG) and diethylene glycol monobutyl ether (BDG) is even more preferred.
[0039] The content of component B in the cleaning agent composition and adhesive remover of this disclosure is preferably 15% by mass or more, more preferably 30% by mass or more, and still preferably 45% by mass or more, from the viewpoint of improving adhesive removeability and compatibility, and preferably 65% by mass or less, more preferably 62.5% by mass or less, and still preferably 60% by mass or less, from the viewpoint of improving adhesive removeability. More specifically, the content of component A in the cleaning agent composition and adhesive remover of this disclosure 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 still preferably 45% by mass or more and 60% by mass or less. When component B is a combination of two or more types, the content of component B refers to the total content of those types.
[0040] The mass ratio A / B of the content of component A to the content of component B is preferably 0.6 or higher, more preferably 0.625 or higher, and even more preferably 0.65 or higher, and from the viewpoint of cleanliness and stability, it is preferably 5.5 or lower, more preferably 3 or lower, and even more preferably less than 1. More specifically, the mass ratio A / B is preferably 0.6 or higher and 5.5 or lower, more preferably 0.625 or higher and 3 or lower, and even more preferably 0.65 or higher and less than 1.
[0041] <Water (component C)> The cleaning agent composition and adhesive remover of this disclosure preferably contain no water or have a water content of 15% by mass or less. Examples of water (hereinafter also referred to as "component C") in one or more embodiments include ion-exchanged water, RO water, distilled water, pure water, ultrapure water, etc. If the cleaning agent composition and adhesive remover of this disclosure contain component C, the content of component C in the cleaning agent composition and adhesive remover of this disclosure may be the remainder after excluding component A, component B, and any optional components described later. Specifically, from the viewpoint of improving adhesive removeability, the content of component C in the cleaning agent composition and adhesive remover of this disclosure is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and essentially 0% by mass (i.e., not included).
[0042] <Other ingredients> The cleaning agent composition and adhesive remover of this disclosure may further contain water (component C) or other components as needed, in addition to components A to B. Examples of other components include those commonly used in cleaning agents, such as 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, and antibacterial agents.
[0043] The cleaning agent composition and adhesive remover of this disclosure preferably do not contain N-methyl-2-pyrrolidone, or contain 1% by mass or less of N-methyl-2-pyrrolidone. If the cleaning agent composition of this disclosure contains N-methyl-2-pyrrolidone, the content of N-methyl-2-pyrrolidone in the cleaning agent composition and adhesive remover of this disclosure is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.01% by mass or less, and essentially 0% by mass (i.e., not included) from the viewpoint of safety such as toxicity and compliance with various regulations.
[0044] In one or more embodiments, the cleaning compositions and adhesive removers of this disclosure may be substantially free of alkanolamines having branched carbon chains. For example, the content of alkanolamines having branched carbon chains in the cleaning compositions and adhesive removers of this disclosure is preferably less than 1% by mass, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0% by mass. In one or more embodiments, the cleaning compositions and adhesive removers of this disclosure may be substantially free of nonionic surfactants. For example, the content of nonionic surfactants in the cleaning compositions and adhesive removers of this 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. Examples of nonionic surfactants include aliphatic hydrocarbons or aromatic hydrocarbons having 8 to 10 carbon atoms to which any ethylene oxide or propylene oxide has been added. In one or more embodiments, the cleaning agent compositions and adhesive removers of this disclosure may 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 agent compositions and adhesive removers of this disclosure is preferably 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0% by mass. In one or more embodiments, the cleaning agent compositions and adhesive removers of this disclosure may be substantially free of hydroxylamine. For example, the hydroxylamine content in the cleaning agent compositions and adhesive removers of this 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. In one or more embodiments, the cleaning agent compositions and adhesive removers of this disclosure may be substantially free of glyoxylic acid. For example, the glyoxylic acid content in the cleaning agent compositions and adhesive removers of this disclosure is preferably less than 0.05% by mass, preferably 0.01% by mass or less, and more preferably 0% by mass. In one or more embodiments, the cleaning agent compositions and adhesive removers of this disclosure may be substantially free of N,N-dimethylacetamine (DMAC). For example, the N,N-dimethylacetamine (DMAC) content in the cleaning agent compositions and adhesive removers of this disclosure is preferably less than 0.1% by mass, preferably 0.01% by mass or less, and more preferably 0% by mass. In one or more embodiments, the cleaning compositions and adhesive removers of this disclosure may be substantially free of quaternary ammonium hydroxides. For example, the content of quaternary ammonium hydroxides in the cleaning compositions and adhesive removers of this disclosure is preferably less than 1% by mass, preferably 0.1% by mass or less, and more preferably 0% by mass.
[0045] [Method for manufacturing a cleaning agent composition and an adhesive remover] The cleaning agent compositions and adhesive removers of this disclosure can be manufactured in one or more embodiments by compounding components A to B and optionally the above-mentioned optional components (component C, other components) in a known manner. For example, the cleaning agent compositions and adhesive removers of this disclosure may consist of at least components A to B. Accordingly, this disclosure relates to a method for manufacturing cleaning agent compositions and adhesive removers, which includes a step of compounding at least components A to B. In this disclosure, "compounding" includes mixing components A to B and optionally the above-mentioned optional components (component C, other components) simultaneously or in any order. In the method for manufacturing cleaning agent compositions and adhesive removers of this disclosure, the preferred amount of each component may be the same as the preferred content of each component of the cleaning agent compositions and adhesive removers of this disclosure described above.
[0046] [Items to be washed] Examples of objects to be cleaned include wafers with adhesive residue. Examples of wafers include semiconductor substrates. Examples of semiconductor substrates include silicon wafers, germanium wafers, gallium-arsenide wafers, gallium-phosphorus wafers, and gallium-arsenide-aluminum wafers. In one or more embodiments, the wafer may also be a substrate having pads and / or lands, which are areas for bonding and mounting. Examples of materials for the pads and lands include metals such as gold and copper. Examples of wafers to which adhesive has adhered include, in one or more embodiments, wafers that have been bonded (fixed) to a fixing member with adhesive and then separated from the fixing member, and wafers that have been bonded (fixed) to a fixing member with adhesive and then subjected to a heat treatment at a temperature of 230°C or higher and then separated from the fixing member. Accordingly, in one embodiment, this disclosure relates to the use of the cleaning agent composition or adhesive remover of this disclosure as a cleaning agent for removing adhesive remaining on a wafer after a wafer bonded (fixed) to a fixing member with adhesive has been separated from the fixing member. In one or more embodiments, the wafer bonded (fixed) to the fixing member with adhesive has been subjected to a heat treatment at a temperature of 230°C or higher. In one or more embodiments, the heat treatment is a heat treatment in a processing step described later. In one or more embodiments, wafers to which adhesive is attached include wafers to which adhesive used in the manufacturing process of three-dimensional integrated circuits (3DICs) is attached. Accordingly, in one embodiment, this disclosure relates to the use of the cleaning agent composition or adhesive remover of this disclosure as a cleaning agent for removing adhesive used in the manufacturing process of three-dimensional integrated circuits. In one or more embodiments, the wafer to which the adhesive is attached has been subjected to a heat treatment at a temperature of 230°C or higher. In one or more embodiments, this heat treatment may include a heat treatment in a processing step described later.
[0047] [Washing method] This disclosure relates to a cleaning method (hereinafter also referred to as "the cleaning method of this disclosure") in which, in one embodiment, a wafer that has been bonded to a fixed member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher is separated from the fixed member, and the adhesive remaining on the wafer is removed with a cleaning agent (cleaning step), wherein the cleaning agent is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether represented by the above formula (I) (component B), 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 of this disclosure described above or an adhesive remover. The cleaning method (adhesive removal method) in the cleaning step of the cleaning method of this disclosure is the same as the cleaning method (removal method) in step (5) of the semiconductor substrate manufacturing method of this disclosure described above. In the cleaning method of this disclosure, the wafer, which is bonded to a fixing member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher, is preferably subjected to a heat treatment at a temperature of 270°C or higher in one or more embodiments. Examples of heat treatment at a temperature of 230°C or higher include heat treatment for joining a substrate on which a circuit is formed to a substrate on which a device such as a semiconductor chip and another substrate on which a circuit is formed, using solder or metal fine particles. The heat treatment step is 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 this disclosure is a wafer after going through steps (1) to (4) of the semiconductor substrate manufacturing method of this disclosure.
[0048] [kit] This disclosure relates, in one embodiment, to a kit (hereinafter also referred to as the "Kit of the Disclosure") for use in either the cleaning method of the Disclosure or the semiconductor substrate manufacturing method of the Disclosure. The Kit of the Disclosure is, in one or more embodiments, a kit for manufacturing the cleaning agent composition or adhesive remover of the Disclosure. According to the Kit of the Disclosure, a cleaning agent composition or adhesive remover with excellent adhesive removal properties can be obtained.
[0049] In one or more embodiments, the kit of this disclosure includes a kit (two-component detergent composition) containing a solution containing component A (first solution) and a solution containing component B (second solution), which are mixed separately and mixed at the time of use. After the first and second solutions are mixed, they may be diluted with water (component C) as needed. Each of the first and second solutions may optionally contain the above-mentioned optional components. [Examples]
[0050] The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited in any way by these examples.
[0051] 1. Preparation of the detergent compositions of Examples 1-3 and Comparative Example 1 The detergent compositions of Examples 1-3 and Comparative Example 1 were prepared by blending each component shown in Table 1 in the amounts (mass %) and effective content listed in Table 1, and then stirring and mixing them.
[0052] The following materials were used to prepare the detergent compositions of Examples 1-3 and Comparative Example 1. (Component A) Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.] (Component B) BDG: Butyl diglycol [manufactured by Nippon Emulsifier Co., Ltd., diethylene glycol monobutyl ether] BG: Butyl glycol [manufactured by Nippon Emulsifier Co., Ltd., ethylene glycol monobutyl ether] (Non-ingredient B) Dipropylene glycol dimethyl ether [manufactured by Nippon Emulsifier Co., Ltd.] (Component C) Water [Pure water with a purity of 1 μS / cm or less, produced using the G-10DSTSET pure water system manufactured by Organo Corporation]
[0053] 2. Evaluation of the detergent compositions of Examples 1-3 and Comparative Example 1 The detergent compositions prepared in Examples 1-3 and Comparative Example 1 were evaluated as follows.
[0054] [Evaluation of cleanability (adhesive removal capability)] Add 200 mL of the cleaning agent compositions of Examples 1-3 and Comparative Example 1 to a 200 mL beaker, and immerse the test piece in the cleaning agent composition at room temperature (25°C) for 10 minutes. Then, remove the test piece from the cleaning agent composition, rinse it with PGME: 1-methoxy-2-propanol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade] and butyl glycol [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., first grade] for about 20 seconds at room temperature, and then allow it to stand and dry at room temperature. The cleaning rate was calculated by visually observing whether any adhesive residue remained on the test pieces, and the cleaning performance (adhesive removal efficiency) was evaluated based on the following evaluation criteria. The results are shown in Table 1. Cleaning rate (%) = (Area from which adhesive was removed after cleaning) / (Area of the test piece) × 100 <Evaluation Criteria> A: Visual inspection reveals no residue or residue area is less than 1%. B: Visual observation shows that the residue area is between 1% and less than 25%. C: Visual observation shows that the residue area is between 25% and less than 40%. D: Visual observation shows that the residue area is between 40% and less than 50%. E: Visual observation shows that the residue area is 50% or more. The test pieces were 30mm x 30mm in size and had adhesive residue on a silicon wafer. The adhesive residue was 20μm thick and present across the entire surface of the test piece. The adhesive used was applied to the test piece and then heat-treated under nitrogen at 250°C for 60 minutes. A polyimide-based adhesive was used.
[0055] [Evaluation of Al electrode damage] Add 100 mL of the cleaning agent compositions of Examples 1-3 and Comparative Example 1 to a 100 mL beaker and heat to 60°C. Immerse the test piece in the 60°C cleaning agent composition for 30 minutes while applying ultrasonic waves (40 kHz, 360 W) using an ultrasonic cleaner (AS ONE Corporation, ASU-20M). Then, remove the test piece from the cleaning agent composition, rinse it with ethanol (Fujifilm Wako Pure Chemical Industries, Ltd., special grade) for about 20 seconds at room temperature, and then allow it to dry at room temperature. Using an optical microscope, the "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), the test pieces after the cleaning test were magnified 100 times and visually inspected, and the damage to the Al electrode was evaluated based on the evaluation criteria below. The results are shown in Table 1. The test piece measures 15mm x 15mm and has 3mm x 2.5mm Al electrodes placed seamlessly on a silicon wafer. <Evaluation Criteria> A: No discoloration is observed in the electrodes. B: No discoloration is observed on the electrodes, but the gloss is slightly reduced. C: No discoloration is observed on the electrode, but the gloss has decreased. D: Discoloration is observed on the electrode.
[0056] [Table 1]
[0057] As shown in Table 1, the cleaning agent compositions of Examples 1 to 3 were found to have superior adhesive removal capabilities compared to Comparative Example 1, which does not contain component B. Furthermore, while Al electrodes can be damaged by polar solvents, the cleaning agent compositions of Examples 1 to 3 were found to suppress damage to Al electrodes. In addition, since the cleaning agent compositions of Examples 1 to 3 do not contain N-methyl-2-pyrrolidone, they can be considered highly safe cleaning agent compositions. [Industrial applicability]
[0058] This disclosure provides a cleaning agent composition that exhibits excellent adhesive removal properties. Furthermore, by using the cleaning agent composition of this disclosure, the productivity of semiconductor substrates can be improved. [Explanation of symbols]
[0059] 1 Fixing member 2. Adhesive 2a Adhesive residue 3 wafers 3a Polished and processed surface of the wafer
Claims
1. (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 above step (3) includes heat treatment of the wafer fixed to the fixing member with adhesive at a temperature of 230°C or higher. A method for manufacturing a semiconductor substrate, wherein the cleaning agent used in step (5) is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)n-H (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n is the number of moles of EO added, which is between 1 and 3.
2. The process includes separating a wafer, which has been bonded to a fixing member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher, 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 is a cleaning agent composition containing an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), wherein the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)n-H (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n is the number of moles of EO added, which is between 1 and 3.
3. A cleaning agent composition for removing adhesive residue from a heat-treated wafer, It contains an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), A cleaning agent composition for adhesives, wherein the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)n-H (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n is the number of moles of EO added, which is between 1 and 3.
4. The detergent composition according to claim 3, which contains no water or has a water content of 15% by mass or less.
5. The detergent composition according to claim 3, wherein the content of component B is 15% by mass or more and 65% by mass or less.
6. The detergent composition according to claim 3, wherein component A 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.
7. The detergent composition according to claim 3, 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 agent 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 residue from a heat-treated wafer, It contains an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), An adhesive remover having a content of component A of 35% by mass or more and 85% by mass or less. RO-(EO)n-H (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n is the number of moles of EO added, which is between 1 and 3.
10. The process includes separating a wafer, which has been bonded to a fixing member with an adhesive and subjected to a heat treatment at a temperature of 230°C or higher, from the fixing member, and then removing any remaining adhesive from the wafer with an adhesive remover. A cleaning method wherein the adhesive remover contains an alkanolamine (component A) and a glycol ether represented by the following formula (I) (component B), and the content of component A is 35% by mass or more and 85% by mass or less. RO-(EO)n-H (I) In the above formula (I), R represents an alkyl group having 1 to 4 carbon atoms, EO represents an ethyleneoxy group, and n is the number of moles of EO added, which is between 1 and 3.