Semiconductor substrate cleaning method, production method for processed semiconductor substrate, and cleaning composition

Abstract

Provided are a semiconductor substrate cleaning method and the like that make it possible to use a cleaning composition to remove (clean) an adhesive residue from the surface of a semiconductor substrate that includes an electrode without damaging the electrode.　A semiconductor substrate cleaning method according to the present invention includes a step for using a cleaning composition to clean a semiconductor substrate that includes an electrode. The value of the polarity parameter (δp) of the Hansen solubility parameters (HSP) of the cleaning composition is less than 9.9 MPa0.5.

Description

Method for cleaning semiconductor substrates, method for producing processed semiconductor substrates, and cleaning composition

[0001] The present invention relates to a method for cleaning a semiconductor substrate, a method for producing a processed semiconductor substrate, and a cleaning composition.

[0002] Semiconductor wafers have traditionally been integrated in a two-dimensional plane, but for the purpose of further integration, semiconductor integration technology is required that integrates (stacks) the plane in a three-dimensional plane as well. This three-dimensional stacking is a technology that integrates multiple layers while connecting them using through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the backside), and the thinned semiconductor wafers are stacked.

[0003] Semiconductor wafers (herein referred to simply as wafers) before thinning are bonded to a support substrate for polishing in a polishing machine. This bond is called a temporary bond because it must be easily removable after polishing. This temporary bond must be easily removed from the support substrate; applying a large force during removal can cause the thinned semiconductor wafer to break or deform. To prevent this, the temporary bond must be easily removed. However, it is undesirable for the temporary bond to become dislodged or shifted due to polishing stress during backside polishing. Therefore, the performance required for the temporary bond is to withstand the stress during polishing and be easily removed after polishing. For example, it must have high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the direction perpendicular to the planar direction during removal, i.e., the vertical direction.

[0004] Under these circumstances, polysiloxane adhesives that can provide these properties are primarily used as temporary adhesives in the semiconductor field. In polysiloxane-based bonding using a polysiloxane adhesive, adhesive residue often remains on the substrate surface after the thinned substrate is peeled off. To avoid problems in subsequent processes, cleaning compositions have been developed to remove this residue and clean the semiconductor substrate surface (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and Patent Document 2 discloses a cured resin remover containing an alkyl ammonium fluoride. However, in the semiconductor field today, there is always a demand for new cleaning compositions, and there is always a demand for effective cleaning compositions and cleaning methods.

[0005] International Publication No. 2014 / 092022 U.S. Patent No. 6,818,608

[0006] However, it has been found that when adhesive residues on a semiconductor substrate having electrodes are removed from the surface of the substrate using a cleaning composition, the electrodes may be damaged. As a result of studying cleaning compositions, the present inventors have found that the degree of damage to the electrodes varies depending on the polarity of the cleaning composition.

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for cleaning a semiconductor substrate, which, when attempting to remove adhesive residue on a semiconductor substrate having electrodes from the substrate surface using a cleaning composition, can remove (clean) adhesive residue from the substrate surface without damaging the electrodes, a method for producing a processed semiconductor substrate that includes such a cleaning method, and a composition for use in such a cleaning method.

[0008] As a result of intensive research into solving the above problems, the present inventors have discovered that by cleaning an adhesive layer such as adhesive residue on a semiconductor substrate having electrodes, particularly an adhesive layer that is a cured film obtained from a siloxane-based adhesive containing a polyorganosiloxane component (A') that cures by a hydrosilylation reaction, using a cleaning composition exhibiting a specific polarity value, the adhesive layer can be successfully removed from the semiconductor substrate without damaging the electrodes, and have completed the present invention.

[0009] That is, the present invention includes the following aspects: [1] A method for cleaning a semiconductor substrate, comprising a step of cleaning a semiconductor substrate having an electrode with a cleaning composition, wherein the value of the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa or less. ０．５[2] The method for cleaning a semiconductor substrate according to [1], wherein the semiconductor substrate having an electrode is a semiconductor substrate obtained by processing a semiconductor substrate in a laminate including the semiconductor substrate having the electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition, and then separating the support substrate from the semiconductor substrate. [3] The method for cleaning a semiconductor substrate according to [2], wherein the adhesive composition contains an adhesive component (S) including at least one adhesive selected from the group consisting of a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive. [4] The method for cleaning a semiconductor substrate according to [3], wherein the adhesive component (S) contains a siloxane-based adhesive. [5] The method for cleaning a semiconductor substrate according to [4], wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that cures by a hydrosilylation reaction. [6] A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate comprising a semiconductor substrate having an electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the support substrate from the semiconductor substrate; and a fourth step of cleaning the semiconductor substrate after separation with a cleaning composition, wherein the value of the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa. ０．５[7] A method for producing a processed semiconductor substrate according to [6], wherein the adhesive composition contains an adhesive component (S) containing at least one selected from a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive. [8] A method for producing a processed semiconductor substrate according to [7], wherein the adhesive component (S) contains a siloxane-based adhesive. [9] A method for producing a processed semiconductor substrate according to [8], wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

[10] A cleaning composition used for cleaning a semiconductor substrate having an electrode, wherein the value of the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa or less. ０．５ a cleaning composition having a viscosity of less than 1000 psig.

[11] The cleaning composition according to

[10] , wherein the semiconductor substrate having an electrode is a semiconductor substrate obtained by processing a semiconductor substrate in a laminate including a semiconductor substrate having an electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition, and then separating the support substrate from the semiconductor substrate.

[12] The cleaning composition according to

[11] , wherein the adhesive composition contains an adhesive component (S) including at least one adhesive selected from the group consisting of a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

[13] The cleaning composition according to

[12] , wherein the adhesive component (S) contains a siloxane-based adhesive.

[14] The cleaning composition according to

[13] , wherein the siloxane-based adhesive contains a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

[0010] The present invention can provide a method for cleaning a semiconductor substrate, which, when attempting to remove adhesive residues on a semiconductor substrate having electrodes from the substrate surface using a cleaning composition, can remove (clean) adhesive residues from the substrate surface without damaging the electrodes, a method for producing a processed semiconductor substrate that includes such a cleaning method, and a composition used in such a cleaning method.

[0011] The present invention will be described in detail below. Note that the following explanation of the constituent elements is an example for explaining the present invention, and the present invention is not limited to these contents.

[0012] (Method for cleaning a semiconductor substrate) The method for cleaning a semiconductor substrate of the present invention includes a step of cleaning a semiconductor substrate having an electrode with a cleaning composition. The cleaning composition has a polarity term (δp) value in the Hansen solubility parameter (HSP) of the cleaning composition of 9.9 MPa. ０．５ is less than.

[0013] In the semiconductor substrate cleaning method of the present invention, a more preferred embodiment of the semiconductor substrate having an electrode to be subjected to the cleaning step is a semiconductor substrate obtained by processing a semiconductor substrate in a laminate comprising a semiconductor substrate having an electrode, a support substrate, and an adhesive layer formed from an adhesive composition between the semiconductor substrate and the support substrate, followed by separating the support substrate from the semiconductor substrate. In this embodiment, the semiconductor substrate obtained by separating the support substrate from the semiconductor substrate can be cleaned using the cleaning composition of the present invention. In this embodiment, if an adhesive layer remains on the semiconductor substrate after separation of the support substrate from the semiconductor substrate, the adhesive residue can be cleaned using the cleaning composition. Furthermore, even if the adhesive layer is not completely removed when the support substrate is separated from the semiconductor substrate, leaving most of the adhesive layer remaining on the semiconductor substrate, the adhesive layer on the semiconductor substrate can be cleaned using the cleaning composition. Alternatively, when the support substrate is separated from the semiconductor substrate, the adhesive layer may be almost completely removed, and it may appear that almost no adhesive residue remains on the semiconductor substrate. However, even in such cases, there may be a very small amount of adhesive residue remaining, and there is also a desire to thoroughly clean the semiconductor substrate surface. Regardless of the amount of adhesive residue, there is always a desire to clean the separated semiconductor substrate. Therefore, regardless of the amount of adhesive layer or adhesive residue present on the semiconductor substrate, any separated semiconductor substrate obtained by separating the support substrate and the semiconductor substrate can be cleaned using the cleaning method of the present invention.

[0014] <Semiconductor Substrate> The semiconductor substrate according to the present invention has electrodes. For example, as described below, it may be a semiconductor substrate having bumps, which are protruding connection electrodes. The main material constituting the entire semiconductor substrate is not particularly limited as long as it is suitable for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors. The shape of the semiconductor substrate is not particularly limited, and may be, for example, a disk. Note that the surface of a disk-shaped semiconductor substrate does not need to be perfectly circular; for example, the outer periphery of the semiconductor substrate may have a straight portion called an orientation flat or a notch. The thickness of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 500 to 1,000 μm. The diameter of the disk-shaped semiconductor substrate may be determined appropriately depending on the intended use of the semiconductor substrate, and is not particularly limited, and is, for example, 100 to 1,000 mm.

[0015] The semiconductor substrate may have bumps. Bumps are protruding terminals. In a laminate, when the semiconductor substrate has bumps, the bumps are located on the support substrate side. In a semiconductor substrate, the bumps are typically formed on the surface on which the circuit is formed. The circuit may be single-layered or multi-layered. The shape of the circuit is not particularly limited. In a semiconductor substrate, the surface opposite to the surface having the bumps (the back surface) is the surface used for processing. The material, size, shape, structure, and density of the bumps on the semiconductor substrate are not particularly limited. Examples of bumps include ball bumps, printed bumps, stud bumps, and plated bumps. The height, radius, and pitch of the bumps are typically determined appropriately based on the following conditions: a bump height of approximately 1 to 200 μm, a bump radius of 1 to 200 μm, and a bump pitch of 1 to 500 μm. Examples of bump materials include low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. The bump may be composed of only a single component or multiple components. More specifically, examples include alloy platings mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps. The bump may also have a laminate structure including a metal layer composed of at least one of these components.

[0016] An example of a semiconductor substrate is a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm.

[0017] The semiconductor substrate of the present invention is applicable to any substrate having electrodes and usable in the semiconductor field. For example, an electronic device substrate having various mechanical structures and circuits formed on the surface of a semiconductor substrate, more specifically, a substrate having an electronic device formed of a layer in which multiple semiconductor chip substrates are embedded in a sealing resin, is also a semiconductor substrate that is applicable to the present invention.

[0018] <Adhesive Layer> The adhesive layer on the semiconductor substrate is formed from an adhesive composition. The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S). Such adhesive component (S) is not particularly limited as long as it is used for this type of application, and examples include siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives. Among these, siloxane-based adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesive properties during processing of wafers, etc., are suitable for peeling after processing, and also have excellent heat resistance.

[0019] <<Adhesive Composition>> In a preferred embodiment, the adhesive composition used in the present invention contains, as an adhesive component, an adhesive component (A) that cures via a hydrosilylation reaction. In a preferred embodiment, the adhesive composition used in the present invention also contains a polyorganosiloxane. The adhesive component (A) may be a component that cures via a hydrosilylation reaction, or a polyorganosiloxane component (A') that cures via a hydrosilylation reaction. In another preferred embodiment, the adhesive component (A) contains, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of the polyorganosiloxane component (A'), a polyorganosiloxane (a2) having a Si—H group, and a platinum group metal catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group. In another preferred embodiment, the polyorganosiloxane component (A') that cures via a hydrosilylation reaction is SiO ２ Siloxane units (Q units) represented by R １ R ２ R ３ SiO １／２ Siloxane units (M units) represented by R ４ R ５ SiO ２／２Siloxane units (D units) represented by the formula: and R ６ SiO ３／２ and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) contains one or more siloxane units (T units) represented by the formula: ２ Siloxane units (Q′ units) represented by R １ 'R ２ 'R ３ 'SiO １／２ Siloxane units (M′ units) represented by R ４ 'R ５ 'SiO ２／２ Siloxane units (D′ units) represented by the formula: ６ 'SiO ３／２ and a polyorganosiloxane (a1') containing at least one siloxane unit selected from the group consisting of M' units, D' units, and T' units, and SiO ２ Siloxane units (Q″ units) represented by R １ "R ２ "R ３ "SiO １／２ Siloxane units (M″ units) represented by R ４ "R ５ "SiO ２／２ Siloxane units (D″ units) represented by the formula: ６ "SiO ３／２ and a polyorganosiloxane (a2') containing one or more siloxane units selected from the group consisting of siloxane units (T" units) represented by the following formula: and at least one siloxane unit selected from the group consisting of M" units, D" units, and T" units. Note that (a1') is an example of (a1), and (a2') is an example of (a2).

[0020] R １ ~R ６are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, and a heteroaryl group.

[0021] R １ '~R ６ R ′ is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group. １ '~R ６ At least one of the groups ' is an alkenyl group which may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0022] R １ "~R ６ " are groups or atoms bonded to the silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but R １ "~R ６ At least one of " is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

[0023] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0024] Specific examples of the optionally substituted straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a tertiary butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a 27-methyl-n-pentyl group, a 2 Examples of such alkyl groups include, but are not limited to, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl groups, and the number of carbon atoms is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Of these, a methyl group is particularly preferred.

[0025] Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a cyclohexyl group, a cyclopent ...

[0044] Examples of cycloalkyl groups include cycloalkyl groups such as 1-n-ethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these. The number of carbon atoms in the cycloalkyl groups is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

[0026] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0027] Specific examples of optionally substituted linear or branched alkenyl groups include, but are not limited to, vinyl, allyl, butenyl, and pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Of these, ethenyl and 2-propenyl groups are particularly preferred. Specific examples of optionally substituted cyclic alkenyl groups include, but are not limited to, cyclopentenyl and cyclohexenyl, and the number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.

[0028] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1') and the polyorganosiloxane (a2'), and the alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') form a crosslinked structure by a hydrosilylation reaction with the platinum group metal catalyst (A2), and then the crosslinked structure is cured. As a result, a cured film is formed.

[0029] The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0030] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include, but are not limited to, (Q' units and M' units), (D' units and M' units), (T' units and M' units), and (Q' units, T' units and M' units).

[0031] In addition, when two or more types of polyorganosiloxanes are included in the polyorganosiloxane (a1'), a combination of (Q' units and M' units) and (D' units and M' units), a combination of (T' units and M' units) and (D' units and M' units), a combination of (Q' units, T' units and M' units) and (T' units and M' units) is preferred, but is not limited to these.

[0032] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0033] Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units and T" units include, but are not limited to, (M" units and D" units), (Q" units and M" units), and (Q" units, T" units and M" units).

[0034] The polyorganosiloxane (a1') is composed of siloxane units in which alkyl groups and / or alkenyl groups are bonded to the silicon atoms thereof. １ '~R ６ The proportion of alkenyl groups in all the substituents represented by R ′ is preferably 0.1 to 50.0 mol %, more preferably 0.5 to 30.0 mol %, and the remaining R １ '~R ６ ' can be an alkyl group.

[0035] The polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and / or a hydrogen atom is bonded to the silicon atom. １ "~R ６ The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R １ "~R ６ " can be an alkyl group.

[0036] When the adhesive component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si—H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0037] The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but is usually 500 to 1,000,000, and from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000. In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane can be measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H manufactured by Tosoh Corporation), a column temperature of 40 ° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 0.35 mL / min, and polystyrene (Shodex manufactured by Showa Denko K.K.) as a standard sample.

[0038] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, but are usually 10 to 1,000,000 (mPa s), and from the viewpoint of realizing the effects of the present invention with good reproducibility, are preferably 50 to 20,000 (mPa s). The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values ​​measured at 25 ° C. using an E-type rotational viscometer.

[0039] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film by hydrosilylation, and therefore the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as an alkyloxy group.

[0040] In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A2) in addition to the polyorganosiloxane component (A'). Such a platinum group metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si—H groups of the polyorganosiloxane (a2).

[0041] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, and platinum bisacetoacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum. The amount of the platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm relative to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0042] The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction. The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction, and specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. The amount of the polymerization inhibitor is not particularly limited, but is usually 1000.0 ppm or more relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and 10,000.0 ppm or less from the viewpoint of preventing excessive suppression of the hydrosilylation reaction.

[0043] The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present invention, the resulting adhesive layer can be effectively and reproducibly released. A typical example of such a release agent component (B) is polyorganosiloxane. The polyorganosiloxane used as the release agent component usually does not react with the adhesive component. For example, the polyorganosiloxane used as the release agent component is a component that does not undergo a hydrosilylation reaction. In a preferred embodiment, specific examples include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes. In another preferred embodiment, the release agent component (B) is polydimethylsiloxane, which may be modified. Examples of the polydimethylsiloxane that may be modified include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

[0044] The weight-average molecular weight of the polyorganosiloxane serving as the release agent component (B) is not particularly limited, but is typically 100,000 to 2,000,000. From the viewpoint of reproducibly achieving the effects of the present invention, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, the dispersity is not particularly limited, but is typically 1.0 to 10.0. From the viewpoint of reproducibly achieving suitable release, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. The weight-average molecular weight and dispersity can be measured using the method described above for polysiloxanes. The complex viscosity of the polyorganosiloxane serving as the release agent component (B) can be measured at 25°C using a rheometer (e.g., an Anton Paar MCR-302 rheometer).

[0045] Examples of epoxy group-containing polyorganosiloxanes include R １１ R １２ SiO ２／２The siloxane unit (D １０ Examples include those containing units.

[0046] R １１ is a group bonded to a silicon atom and represents an alkyl group; R １２ is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include the examples mentioned above. The epoxy group in the organic group containing an epoxy group may be an independent epoxy group without being condensed with another ring, or may be an epoxy group that forms a condensed ring with another ring, such as a 1,2-epoxycyclohexyl group. Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl. In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is, but is not limited to, epoxy group-containing polydimethylsiloxane.

[0047] The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D １０ units), but D １０ In addition to the units, the epoxy group-containing polyorganosiloxane may contain Q units, M units and / or T units. In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include D １０ Polyorganosiloxane consisting only of units, D １０ polyorganosiloxanes containing D units and Q units; １０ Polyorganosiloxanes containing D units and M units, １０ Polyorganosiloxanes containing D units and T units, １０ polyorganosiloxanes containing units, Q units and M units, １０ Polyorganosiloxanes containing units, M units and T units, D １０ Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0048] The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. The weight average molecular weight is not particularly limited, but is usually 1,500 to 500,000, and from the viewpoint of suppressing precipitation in the adhesive, is preferably 100,000 or less.

[0049] Specific examples of epoxy group-containing polyorganosiloxanes include, but are not limited to, those represented by formulas (E1) to (E3).

[0050] (m １ and n １ indicates the number of each repeating unit and is a positive integer.)

[0051] (m ２ and n ２ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0052] (m ３ , n ３ and ３ indicates the number of each repeating unit and is a positive integer, and R is an alkylene group having 1 to 10 carbon atoms which may be interrupted by at least one of an oxygen atom and an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond, or -N=N-).

[0053] Examples of the methyl group-containing polyorganosiloxane include R ２１０ R ２２０ SiO ２／２ The siloxane unit (D ２００ units), preferably R ２１ R ２１ SiO ２／２ The siloxane unit (D ２０ Examples include those containing units.

[0054] R ２１０ and R ２２０are groups bonded to a silicon atom, and each independently represents an alkyl group, at least one of which is a methyl group. Specific examples of the alkyl group include those listed above. ２１ is a group bonded to a silicon atom, and represents an alkyl group, and specific examples of the alkyl group include those listed above. ２１ In the present invention, a preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

[0055] The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D ２００ Unit or D ２０ units), but D ２００ Units and D ２０ In addition to units, Q units, M units and / or T units may be included.

[0056] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D ２００ Polyorganosiloxane consisting only of units, D ２００ polyorganosiloxanes containing D units and Q units; ２００ Polyorganosiloxanes containing D units and M units, ２００ Polyorganosiloxanes containing D units and T units, ２００ polyorganosiloxanes containing units, Q units and M units, ２００ Polyorganosiloxanes containing units, M units and T units, D ２００ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0057] In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D ２０ Polyorganosiloxane consisting only of units, D ２０ polyorganosiloxanes containing D units and Q units; ２０ Polyorganosiloxanes containing D units and M units, ２０ Polyorganosiloxanes containing D units and T units, ２０polyorganosiloxanes containing units, Q units and M units, ２０ Polyorganosiloxanes containing units, M units and T units, D ２０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0058] Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, those represented by formula (M1).

[0059] (n ４ indicates the number of repeating units and is a positive integer.)

[0060] Examples of the phenyl group-containing polyorganosiloxane include R ３１ R ３２ SiO ２／２ The siloxane unit (D ３０ Examples include those containing units.

[0061] R ３１ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R ３２ is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0062] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D ３０ units), but D ３０ In addition to units, Q units, M units and / or T units may be included.

[0063] In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include D ３０ Polyorganosiloxane consisting only of units, D ３０ polyorganosiloxanes containing D units and Q units; ３０ Polyorganosiloxanes containing D units and M units, ３０ Polyorganosiloxanes containing D units and T units, ３０ polyorganosiloxanes containing units, Q units and M units, ３０ Polyorganosiloxanes containing units, M units and T units, D３０ Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0064] Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

[0065] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0066] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0067] The polyorganosiloxane of the release agent component (B) may be a commercially available product or may be synthesized. Commercially available polyorganosiloxanes include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST GUM, which are products manufactured by Wacker Chemie, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy group-containing polyorganosiloxane (trade name CMS-227, ECMS-327) manufactured by Gelest, and Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343), epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., and phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE, but are not limited to these.

[0068] The adhesive composition used in the present invention contains a release agent component (B) in addition to the curable component (A), and in a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.

[0069] An example of the adhesive composition used in the present invention can contain the curable component (A) and the release agent component (B) in any ratio, but considering the balance between adhesion and releasability, the ratio of the curable component (A) to the release agent component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, in mass ratio [(A):(B)]. That is, when a polyorganosiloxane component (A') that cures by a hydrosilylation reaction is included, the ratio of the component (A') to the release agent component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, in mass ratio [(A'):(B)].

[0070] The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., and specific examples of the solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0071] More specifically, examples of the solvent include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents may be used alone or in combination of two or more.

[0072] When the adhesive composition used in the present invention contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the composition, the coating method to be used, the thickness of the thin film to be produced, etc., but is in the range of about 10 to 90 mass % based on the total mass of the composition.

[0073] The viscosity of the adhesive composition used in the present invention is not particularly limited, but is typically 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness. In the present invention, film-constituting components refer to components other than the solvent contained in the composition.

[0074] An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and, if used, a solvent. The mixing order is not particularly limited, but examples of methods that can easily and reproducibly produce a peeling adhesive composition include, but are not limited to, a method of dissolving component (A) and release agent component (B) in a solvent, or a method of dissolving a portion of component (A) and a portion of release agent component (B) in a solvent and the remaining portion in a solvent, and then mixing the resulting solutions. When preparing the adhesive composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components. In the present invention, the solvent or solution used may be filtered using a filter or the like during the production of the adhesive composition or after all components have been mixed, in order to remove foreign matter.

[0075] The thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining a good peeling effect with good reproducibility, it is preferably 10 to 100 μm, more preferably 20 to 50 μm.

[0076] <Cleaning Composition> The cleaning composition is a composition used to remove an adhesive layer from a semiconductor substrate and to clean the adhesive layer on the semiconductor substrate. The cleaning composition usually contains a solvent. Examples of the solvent include lactones, ketones, polyhydric alcohols, compounds having an ester bond, derivatives of polyhydric alcohols, cyclic ethers, esters, and aromatic organic solvents. Examples of lactones include γ-butyrolactone. Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol. Examples of compounds having an ester bond include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate. Examples of derivatives of polyhydric alcohols include compounds having an ether bond, such as monoalkyl ethers or monophenyl ethers of the above polyhydric alcohols or compounds having an ester bond, such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred. Examples of cyclic ethers include dioxane. Examples of esters include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, and mesitylene.These may be used alone or in combination of two or more.

[0077] <<Characteristics of Cleaning Composition>> The present invention specifies a value relating to the polarity of the cleaning composition. The cleaning composition of the present invention has a polarity parameter (δp) value in the Hansen solubility parameter (HSP) of the cleaning composition of 9.9 MPa. ０．５ As will be shown in the examples below, cleaning compositions that satisfy the above polarity term (δp) value can remove (clean) adhesive residues from the surface of a substrate without damaging the electrodes.

[0078] The polarity term (δp) can be calculated using solubility parameter calculation software (Hansen SP&QSPR model, Winmostar V11, X-Ability Co. Ltd., Tokyo, Japan, 2022) based on the molecular structure information of each component. When the cleaning composition is composed of one type of solvent, the polarity term (δp) is determined using the solubility parameter calculation software as described above. When the cleaning composition is composed of multiple types of solvents, the polarity term (δp) of each solvent is calculated and multiplied by the blending ratio of each solvent to calculate the polarity term (δp) value taking into account the blending ratio of each solvent. The polarity term (δp) values ​​taking into account the blending ratio of each solvent are then added together for all the constituent solvents to determine the polarity term (δp) of the cleaning composition.

[0079] <<Specific examples of components constituting the cleaning composition>> The cleaning composition may contain, for example, the following component [I], and may also contain solvent components such as the following components [II] to [IV]: Component [I]: a quaternary ammonium salt, Component [II]: an amide-based solvent, Component [III]: a solvent represented by the following formula (L),

[0080] (In the formula, L １ and L ２ each independently represents an alkyl group having 2 to 5 carbon atoms; L ３ represents O or S.

[0081] Component [IV]: A solvent represented by the following formula (T) or (G):

[0082] (In the formula, X １ and X ３ are each independently an alkyl group or an acyl group (X ４ —C(═O)—), and X ２ represents an alkylene group, and n represents 2 or 3. ４ represents an alkyl group.

[0083] (In the formula, L 1１ and L １２ each independently represents an alkyl group having 1 to 6 carbon atoms; L 1１ The number of carbon atoms in the alkyl group and L １２ The total number of carbon atoms in the alkyl groups is 7 or less.

[0084] The solvent components of the component [I] and the components [II] to [IV] will be described in more detail below.

[0085] <<<Component [I]: Quaternary Ammonium Salt>>> The cleaning composition of the present invention may or may not contain the quaternary ammonium salt described as component [I]. However, it is preferable to use a cleaning composition containing the quaternary ammonium salt of component [I], as it can better demonstrate the effects of the present invention. When a cleaning composition contains the quaternary ammonium salt of component [I], adhesive residues can be easily removed (cleaned) from the surface of a substrate. On the other hand, when the quaternary ammonium salt of component [I] is contained, damage to electrodes is greater than when the quaternary ammonium salt of component [I] is not contained. Therefore, by using a cleaning composition containing the quaternary ammonium salt of component [I] that exhibits a specific polarity term value specified in the present invention, adhesive residues can be easily removed from the surface of a substrate and damage to electrodes can be prevented.

[0086] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application. The quaternary ammonium salt is effective as a component for dissolving the adhesive layer. A typical example of such a quaternary ammonium cation is a tetra(hydrocarbon)ammonium cation. On the other hand, the anion that forms a pair with the quaternary ammonium cation is a hydroxide ion (OH － ) ; fluorine ion (F － ), chloride ions (Cl － ), bromine ion (Br － ), iodine ion (I － ) and other halogen ions; tetrafluoroborate ion (BF ４ － ) ; hexafluorophosphate ion (PF ６ － ) and the like, but are not limited to these.

[0087] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0088] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms. In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride includes tetraalkylammonium fluoride. Specific examples of tetraalkylammonium fluorides include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride). Of these, tetrabutylammonium fluoride is preferred.

[0089] The quaternary ammonium salt, such as tetra(hydrocarbon)ammonium fluoride, may be used in the form of a hydrate. Furthermore, the quaternary ammonium salt, such as tetra(hydrocarbon)ammonium fluoride, may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition. However, a small amount is preferred because it can effectively prevent damage to dicing tape and the like during the cleaning process. Specifically, the amount is typically 0.1 to 5 mass % of the cleaning composition.

[0090] <<<<Component [II]: Amide-based solvent>>>

[0091] The amide solvent is effective as a component for dissolving the quaternary ammonium salt well and obtaining a cleaning composition with excellent uniformity. The amide solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and no active hydrogen on the nitrogen atom. A suitable example of the amide solvent is an acid amide derivative represented by the following formula (Z):

[0092]

[0093] In the formula, R ０ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. Ａ and R Ｂ each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R Ａ and R Ｂ As the alkyl group, a methyl group or an ethyl group is preferred, and both of them are more preferably methyl groups or ethyl groups, and both of them are even more preferably methyl groups.

[0094] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyric acid amide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

[0095] The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

[0096] Another example of a preferred amide solvent is a compound represented by formula (Y) including a lactam compound.

[0097]

[0098] In formula (Y), R １０１ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R １０２ represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1):

[0099]

[0100] R １０２ Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc., and specific examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., but are not limited to these.

[0101] In formula (Y1), R １０３ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R １０４ represents an alkylene group having 1 to 5 carbon atoms, *1 represents a bond bonded to a carbon atom in formula (Y), and *2 represents a bond bonded to a nitrogen atom in formula (Y).

[0102] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, and δ-lactam compounds, and these can be used alone or in combination of two or more.

[0103] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP). Another preferred embodiment of the compound represented by formula (Y) is, for example, 1,3-dimethyl-2-imidazolidinone.

[0104] Of the components [II], it is more preferable to use an acid amide derivative represented by formula (Z), taking into consideration operational restrictions imposed by regulations regarding the use of chemical substances.

[0105] The content of the amide solvent in the cleaning composition can be 70% by mass or less, based on 100% by mass of the aprotic solvent in the cleaning composition. The content of the amide solvent is preferably 10 to 55% by mass, more preferably 20 to 50% by mass, even more preferably 20 to 45% by mass, and particularly preferably 20 to 40% by mass, based on 100% by mass of the aprotic solvent. In the present invention, the content of the mixed solvent is defined as the ratio relative to 100% by mass of the aprotic solvent, which is a solvent lacking a hydroxyl group (—OH). Therefore, protic solvents such as water, methanol, and 1-methoxy-2-propanol are not included in the content ratio criteria. In the present invention, the aprotic solvent refers to, for example, N,N-dimethylpropionamide, dibutyl ether, dipropylene glycol dimethyl ether, and butyl acetate, and the mixing ratio can be calculated based on the total amount of these solvents.

[0106] <<<Component [III]: Solvent Represented by Formula (L)>>> The solvent represented by the following formula (L) is effective as a component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.

[0107]

[0108] In the above formula (L), L １ and L ２ each independently represents an alkyl group having 2 to 5 carbon atoms; L ３ represents O or S. １ and L ２ may be the same group or different groups, but from the viewpoint of availability, they are preferably the same group.

[0109] The alkyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic. From the viewpoint of achieving reproducible peeling of the adhesive layer in a short time, the alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

[0110] Specific examples of the linear or branched alkyl group include, but are not limited to, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, and an n-pentyl group.

[0111] Specific examples of cyclic alkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, and cyclopentyl groups.

[0112] In order to achieve reproducible peeling of the adhesive layer in a short time, the alkyl group having 2 to 5 carbon atoms is preferably an ethyl group, an n-propyl group, an n-butyl group, or an n-pentyl group, and more preferably an ethyl group, an n-propyl group, or an n-butyl group.

[0113] From the viewpoint of realizing reproducible peeling of the adhesive layer in a shorter time and from the viewpoint of easy availability of the compound, L 1 and L ２ are preferably the same group.

[0114] From the viewpoint of realizing reproducible peeling of the adhesive layer in a shorter time, and from the viewpoint of easy availability of the compound, preferred examples of the organic solvent represented by formula (L) include di(n-butyl) ether, diethyl ether, di(n-pentyl) ether, and di(n-propyl) sulfide.

[0115] The content of the solvent represented by formula (L) in the cleaning composition can be 30% by mass or more, based on 100% by mass of the aprotic solvent in the cleaning composition. The content of the solvent represented by formula (L) in the cleaning composition is preferably 30% by mass or more, more preferably 31% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the aprotic solvent in the cleaning composition. It is preferably 90% by mass or less, and more preferably 80% by mass or less. These upper and lower limits may be in any combination. Therefore, the content of the solvent represented by formula (L) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, based on 100% by mass of the aprotic solvent in the cleaning composition.

[0116] <<<Component [IV]: Solvent Represented by Formula (T) or Formula (G)>>> The solvent represented by formula (T) or formula (G) below is effective as an adjusting component for improving the compatibility between the amide solvent represented by component [II] and the solvent represented by formula (L) represented by component [III] in a cleaning composition containing the quaternary ammonium salt represented by component [I].

[0117]

[0118] In formula (T), X １ and X ３ are each independently an alkyl group or an acyl group (X ４ —C(═O)—), and X ２ represents an alkylene group, and n represents 2 or 3. ４ represents an alkyl group.

[0119] X １ and X ３ Examples of the alkyl group represented by X include alkyl groups having 1 to 4 carbon atoms, and more specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. ２ Examples of the alkylene group represented by X include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and a 1,2-propylene group.４ Examples of the alkyl group represented by X include alkyl groups having 1 to 4 carbon atoms. １ Or X ３ The alkyl groups are the same as those shown below.

[0120] Preferred examples of the solvent represented by formula (T) include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0121]

[0122] In formula (G), L 1１ and L １２ each independently represents an alkyl group having 1 to 6 carbon atoms; L 1１ The number of carbon atoms in the alkyl group and L １２ The total number of carbon atoms in the alkyl groups is 7 or less.

[0123] In the above formula (G), L 1１ and L １２ each independently represents an alkyl group having 1 to 6 carbon atoms, and L 1１ The number of carbon atoms in the alkyl group and L １２ The total number of carbon atoms in the alkyl groups is equal to or less than 7. By using such a number of carbon atoms, peeling of the adhesive layer can be achieved in a short time with good reproducibility.

[0124] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

[0125] Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, and a 3-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.

[0126] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2, Examples of cycloalkyl groups include, but are not limited to, a 2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl-cyclobutyl group, a 3,3-dimethyl-cyclobutyl group, a 1-n-propyl-cyclopropyl group, a 2-n-propyl-cyclopropyl group, a 1-i-propyl-cyclopropyl group, a 2-i-propyl-cyclopropyl group, a 1,2,2-trimethyl-cyclopropyl group, a 1,2,3-trimethyl-cyclopropyl group, a 2,2,3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, and a 2-ethyl-3-methyl-cyclopropyl group.

[0127] From the viewpoint of realizing peeling of the adhesive layer in a shorter time with good reproducibility, 1１ is preferably a methyl group, and １２ is preferably a butyl group or a pentyl group.

[0128] From the viewpoint of achieving reproducible peeling of the adhesive layer in a shorter time and from the viewpoint of easy availability of the compound, preferred examples of the organic solvent represented by formula (G) include butyl acetate and pentyl acetate.

[0129] The content of the solvent represented by formula (T) or formula (G) in the cleaning composition is preferably 0.1 to 60 mass%, more preferably 5 to 40 mass%, even more preferably 5 to 35 mass%, still more preferably 5 to 31 mass% or less, and particularly preferably 5 to 30 mass% or less, based on 100 mass% of the aprotic solvent in the cleaning composition.

[0130] <<Cleaning Step>> The semiconductor substrate cleaning method of the present invention includes a step of cleaning a semiconductor substrate having an electrode with a cleaning composition. A more preferred embodiment of the semiconductor substrate cleaning method of the present invention includes a step of processing a semiconductor substrate in a laminate including a semiconductor substrate having an electrode, a support substrate, and an adhesive layer formed from an adhesive composition and disposed between the semiconductor substrate and the support substrate, followed by separating the support substrate from the semiconductor substrate. The cleaning method includes a step of cleaning the separated semiconductor substrate with a cleaning composition. As described above, there are no particular restrictions on the amount of adhesive layer or adhesive residue present on the semiconductor substrate to be cleaned after separation. By using the semiconductor substrate cleaning method of the present invention, the adhesive layer or adhesive residue present on the semiconductor substrate after separation can be easily removed (cleaned) by using the cleaning composition of the present invention without damaging the electrodes present on the semiconductor substrate. In this specification, when referring to an "adhesive layer or adhesive residue" present on a semiconductor substrate, the adhesive residue may be included in the adhesive layer and may be referred to as the "adhesive layer" present on the semiconductor substrate.

[0131] In the present invention, a cleaning composition is continuously brought into contact with an adhesive layer on a semiconductor substrate. By carrying out this cleaning operation, the adhesive layer can be removed. In the present invention, "removal (cleaning)" refers to the removal of the adhesive layer from the semiconductor substrate, and includes both the case where the adhesive layer swells and peels off from the semiconductor substrate, and the case where the adhesive layer dissolves in a solution and disappears from the semiconductor substrate. The method for continuously contacting the adhesive layer on the semiconductor substrate with the cleaning composition is not particularly limited, as long as the adhesive layer on the semiconductor substrate is in contact with the cleaning composition with temporal continuity. This temporal continuity includes not only cases in which the adhesive layer is in constant contact with the cleaning composition, but also cases in which, for example, the adhesive layer is brought into contact with an organic solvent for a certain period of time, the contact is stopped, and then the contact is resumed or repeated. It also includes not only cases in which the entire adhesive layer on the semiconductor substrate is in contact with the cleaning composition, but also cases in which only a part of the adhesive layer is in contact with the cleaning composition. However, from the viewpoint of achieving more effective cleaning with good reproducibility, an embodiment in which the adhesive layer on the semiconductor substrate is in constant contact with the cleaning composition is preferred, and an embodiment in which the entire adhesive layer on the semiconductor substrate is in contact with the cleaning composition is also preferred.

[0132] Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is removed from the semiconductor substrate by immersing the adhesive layer in a cleaning composition to cause it to swell and dissolve, or by continuously supplying a cleaning composition onto the adhesive layer to cause it to swell and dissolve.

[0133] To immerse the adhesive layer on a semiconductor substrate in a cleaning composition, for example, the semiconductor substrate with the adhesive layer may be immersed in the cleaning composition. The immersion time is the time until the adhesive layer swells and dissolves and peels off from the semiconductor substrate, and is not particularly limited, but is 5 seconds or more from the viewpoint of achieving more effective cleaning with good reproducibility, and 5 minutes or less from the viewpoint of process throughput.

[0134] When the adhesive layer on the semiconductor substrate is immersed in the cleaning composition, removal (cleaning) of the adhesive layer may be promoted by moving the semiconductor substrate with the adhesive layer in the cleaning composition, by causing convection in the cleaning composition, by vibrating the cleaning composition with ultrasound, or the like.

[0135] In order to move a semiconductor substrate with an adhesive layer in a cleaning composition, for example, a swinging cleaner, a paddle-type cleaner, or the like may be used. When such a cleaner is used, the stage on which the semiconductor substrate with an adhesive layer is placed moves or rotates up and down or left and right, causing the adhesive layer on the semiconductor substrate to be subjected to relative convection, or the adhesive layer on the semiconductor substrate to be subjected to convection generated by this movement or rotation, which not only promotes swelling and dissolution of the adhesive layer on the semiconductor substrate but also promotes peeling and dissolution of the adhesive layer from the semiconductor substrate.

[0136] To convect the cleaning composition, in addition to the above-mentioned oscillating cleaner or paddle-type cleaner, for example, a convection cleaner may be used, in which the semiconductor substrate with the adhesive layer is fixed on a stage or the like and the cleaning composition around the substrate is convected by an agitator.

[0137] To vibrate the cleaning composition with ultrasonic waves, an ultrasonic cleaner or an ultrasonic probe may be used, and the vibration conditions are usually 20 kHz to 5 MHz.

[0138] In order to continuously supply the cleaning composition onto the adhesive layer on the semiconductor substrate, the cleaning composition can be continuously applied to the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate faces upward, for example, from above (including diagonally above) the adhesive layer on the semiconductor substrate, a rod-shaped or mist-shaped, preferably rod-shaped, cleaning composition is continuously supplied onto the adhesive layer on the semiconductor substrate using a nozzle or the like of a cleaning device. In this case, the continuous supply of the cleaning composition onto the adhesive layer on the semiconductor substrate does not only include the case where the cleaning composition is constantly supplied onto the adhesive layer on the semiconductor substrate, but also includes, for example, the case where the cleaning composition is supplied for a certain period of time, then the supply is stopped, and then the supply is resumed, or this is repeated. However, from the viewpoint of realizing more effective cleaning with good reproducibility, it is preferable that the cleaning composition is constantly supplied onto the adhesive layer on the semiconductor substrate.

[0139] When the cleaning composition is dispensed in a bar form onto the adhesive layer on the semiconductor substrate, the flow rate is usually 200 to 500 mL / min.

[0140] In one embodiment of the present invention, in order to ensure that the adhesive layer on the semiconductor substrate is constantly in contact with the cleaning composition, the adhesive layer may be brought into contact with the vapor of the cleaning composition, for example, using a steam cleaner.

[0141] The semiconductor substrate cleaning method of the present invention may include a step of removing the peeled adhesive layer. The method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the semiconductor substrate. When a semiconductor substrate with an adhesive layer is immersed in a cleaning composition, the peeled adhesive layer present in the cleaning composition may be removed without removing the semiconductor substrate from the cleaning composition. Alternatively, the semiconductor substrate may be removed from the cleaning composition and the peeled adhesive layer may be removed by separating the semiconductor substrate from the peeled adhesive layer. In this case, simply removing the semiconductor substrate from the cleaning composition may naturally leave the peeled adhesive layer in the cleaning composition, allowing most of it to be removed.

[0142] Specific examples of methods for removing the peeled adhesive layer include, but are not limited to, removing the peeled adhesive layer by adsorption or suction using a device, removing the peeled adhesive layer by blowing it away with gas such as an air gun, and removing the peeled adhesive layer by centrifugal force caused by moving or rotating the semiconductor substrate up and down or left and right.

[0143] After removing the peeled adhesive layer from the semiconductor substrate, the semiconductor substrate is dried, if necessary, according to a standard method.

[0144] (Cleaning Composition) The cleaning composition used in the semiconductor substrate cleaning method of the present invention is also a subject of the present invention. The cleaning composition of the present invention is used to remove (clean) an adhesive layer on a semiconductor substrate from the semiconductor substrate, and preferred embodiments and conditions are as described above. The cleaning composition of the present invention can be produced by mixing the solvents that constitute the composition in any order, if necessary. At this time, filtration or the like may be performed, if necessary.

[0145] (Method for manufacturing processed semiconductor substrate) By using the semiconductor substrate cleaning method of the present invention described above, it is possible to efficiently remove the adhesive layer on the substrate of the semiconductor substrate, particularly the adhesive layer which is a cured film obtained from a siloxane adhesive containing a polyorganosiloxane component (A ') which is cured by a hydrosilylation reaction, and it is possible to expect the production of highly efficient and good semiconductor elements. Furthermore, by using the semiconductor substrate cleaning method of the present invention, when cleaning the semiconductor substrate, especially when removing the adhesive layer on the substrate of the semiconductor substrate, it is also possible to prevent damage to the electrodes.

[0146] The method for producing a processed semiconductor substrate of the present invention can produce a processed semiconductor substrate with a clean surface, for example, by polishing and thinning a semiconductor wafer, separating (peeling) the support substrate from the thinned semiconductor wafer, and then cleaning the semiconductor wafer using the semiconductor substrate cleaning method of the present invention. More preferably, the method for producing a processed semiconductor substrate of the present invention can produce a processed semiconductor substrate with a clean surface (particularly a processed semiconductor substrate with a clean surface free of any remaining adhesive layer), for example, by polishing and thinning a semiconductor wafer, separating (peeling) the support substrate from the thinned semiconductor wafer, and then cleaning (removing) the semiconductor wafer (particularly the adhesive layer remaining on the semiconductor wafer) using the semiconductor substrate cleaning method of the present invention. An example of the use of the semiconductor substrate cleaning method of the present invention in a semiconductor process is its use in a method for producing processed semiconductor substrates, such as thinned ones, used in semiconductor packaging technologies such as TSV.

[0147] The semiconductor substrates to be cleaned by the cleaning method of the present invention include, in addition to the silicon semiconductor substrates such as the silicon wafers described above, various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon nitride film-formed silicon substrates, silicon oxide film-formed silicon substrates, polyimide film-formed silicon substrates, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0148] A preferred embodiment of the method for producing a processed semiconductor substrate of the present invention includes the following steps: a first step: producing a laminate including a semiconductor substrate having an electrode, a support substrate, and an adhesive layer obtained from an adhesive composition and disposed between the semiconductor substrate and the support substrate; a second step: processing the semiconductor substrate of the resulting laminate; a third step: separating the support substrate from the semiconductor substrate; and a fourth step: cleaning the separated semiconductor substrate with a cleaning composition. Here, the cleaning composition is as described above in the section entitled "Cleaning Composition." In the fourth step, the semiconductor substrate cleaning method of the present invention is used. Each step will be described in detail below.

[0149] <Step 1> The adhesive composition used to form the adhesive layer in Step 1 can be any of the various adhesives described above, but the semiconductor substrate cleaning method of the present invention is effective for removing an adhesive layer obtained from a polysiloxane adhesive, and is even more effective for removing an adhesive layer obtained from a polysiloxane adhesive containing an adhesive component (A) that cures by a hydrosilylation reaction. Therefore, below, an example will be described in which an adhesive layer obtained using a polysiloxane adhesive (adhesive composition) is removed using the cleaning method of the present invention when producing a semiconductor substrate processed using the adhesive layer, but the present invention is not limited thereto.

[0150] The first step of producing a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described below.

[0151] In one embodiment, the first step includes a step of applying an adhesive composition to the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer, and a step of joining the semiconductor substrate and the support substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a decompression treatment to bring them into close contact, and then performing a post-heat treatment to form a laminate. In another embodiment, the laminate may have an additional layer (e.g., a release layer) in addition to the semiconductor substrate, the support substrate, and the adhesive layer. For example, in this other embodiment, the first step includes the steps of applying an adhesive composition to the surface of one of the circuit surfaces of a semiconductor substrate wafer or the surface of a support substrate and heating the applied composition to form an adhesive coating layer, applying a release agent composition to the surface of the other substrate other than the substrate on which the adhesive coating layer is formed and heating the applied composition to form a release agent coating layer, and bonding the adhesive coating layer formed on the surface of one of the circuit surfaces of the semiconductor substrate wafer or the surface of the support substrate to the release agent coating layer formed on the surface of the other of the circuit surfaces of the semiconductor substrate wafer or the surface of the support substrate by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. Note that the adhesive composition and the release agent composition are applied to either the circuit surface of the semiconductor substrate wafer or the surface of the support substrate and heated, respectively, but the application and heating of the adhesive composition and the release agent composition may be performed sequentially on either one of the substrates. In each of the above embodiments, whether to adopt the treatment conditions of heat treatment, reduced pressure treatment, or a combination of both is determined in consideration of various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, the desired adhesive strength, etc. In a laminate having a release layer, the order of lamination is not particularly limited, and either a laminate in which a semiconductor substrate, a release layer, an adhesive layer, and a support substrate are laminated in this order, or a laminate in which a semiconductor substrate, an adhesive layer, a release layer, and a support substrate are laminated in this order, may be employed.

[0152] Here, for example, the semiconductor substrate is a wafer and the support substrate is a support body, and the adhesive composition may be applied to either or both of the semiconductor substrate and the support substrate.

[0153] Examples of wafers include, but are not limited to, silicon wafers and glass wafers with a diameter of approximately 300 mm and a thickness of approximately 770 μm. In particular, the semiconductor substrate cleaning method of the present invention can effectively clean semiconductor substrates with bumps. Specific examples of such bumped semiconductor substrates include silicon wafers with bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, which are typically selected from the following conditions: bump height of approximately 1 to 200 μm, bump diameter of 1 to 200 μm, and bump pitch of 1 to 500 μm. Specific examples of plated bumps include, but are not limited to, Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.

[0154] The support substrate (carrier) is not particularly limited, but may be, for example, a silicon wafer with a diameter of about 300 mm and a thickness of about 700 μm, but is not limited to this.

[0155] Stripping compositions include compositions containing stripping components used in this type of application.

[0156] The coating method is not particularly limited, but is usually a spin coating method. Note that a method of forming a coating film by a separate method such as spin coating and attaching a sheet-like coating film may also be employed, and this method is also referred to as coating or coating film.

[0157] The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0158] The heating temperature of the applied release agent composition cannot be generally specified because it differs depending on the types and amounts of crosslinking agent, acid generator, acid, etc., whether or not a solvent is contained, the desired thickness of the release layer, etc., but is 120°C or higher from the viewpoint of achieving suitable curing, and preferably 260°C or lower from the viewpoint of preventing excessive curing, and the heating time is usually 1 to 10 minutes. Heating can be performed using a hot plate, an oven, etc.

[0159] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 μm.

[0160] The thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually 5 to 500 μm.

[0161] The heat treatment temperature is typically determined appropriately from the range of 20 to 150° C., taking into consideration the need to soften the adhesive coating layer to achieve favorable bonding, the need to soften the adhesive coating layer to achieve favorable bonding with the release agent coating layer, and the need to achieve favorable curing of the release agent coating layer. In particular, from the perspective of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component or release agent component, the heat treatment temperature is preferably 130° C. or lower, more preferably 90° C. or lower, and the heating time is typically 30 seconds or longer, preferably 1 minute or longer, from the perspective of ensuring the adhesive ability is fully exerted, but is typically 10 minutes or shorter, preferably 5 minutes or shorter, from the perspective of suppressing deterioration of the adhesive layer and other members.

[0162] The reduced pressure treatment may be carried out by exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0163] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together, preferably by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0164] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers therebetween and can firmly bring them into close contact with each other, but is usually within the range of 10 to 1000 N.

[0165] The post-heating temperature is preferably 120°C or higher from the viewpoint of obtaining a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate, adhesive component, release agent component, etc. The heating time is usually 1 minute or longer from the viewpoint of achieving suitable wafer bonding by curing, and preferably 5 minutes or longer from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be carried out using a hot plate, oven, etc. One purpose of the post-heating treatment is to more suitably cure the adhesive component (S).

[0166] <Second Step> Next, the second step of processing the semiconductor substrate of the laminate obtained by the method described above will be described. One example of processing performed on the laminate used in the present invention is processing the back surface of the semiconductor substrate, opposite the circuit surface on the front surface. Typically, this involves thinning the wafer by polishing the back surface of the wafer. Using such a thinned wafer, through-silicon vias (TSVs) and the like are formed, and then the thinned wafer is peeled off from the support substrate to form a wafer stack, which is then three-dimensionally packaged. Also, before and after this, wafer backside electrodes and the like are formed. During the wafer thinning and TSV process, heat of 250 to 350°C is applied while the wafer is bonded to the support substrate, and the adhesive layer contained in the laminate used in the present invention is heat-resistant to this heat. For example, a wafer with a diameter of approximately 300 mm and a thickness of approximately 770 μm can be thinned to a thickness of approximately 80 to 4 μm by polishing the back surface, opposite the circuit surface on the front surface.

[0167] <Third Step> The third step of separating the processed semiconductor substrate from the support substrate will be described. In the third step, the processed semiconductor substrate is separated from the support substrate. The method for separating the processed semiconductor substrate from the support substrate can be performed by peeling between the adhesive layer and the semiconductor substrate or support substrate in contact therewith. Examples of such peeling methods include, but are not limited to, laser peeling, mechanical peeling using a tool with a sharp part, and manual peeling.

[0168] <Fourth Step> Next, the fourth step of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described. The fourth step is a step of cleaning the semiconductor substrate using the semiconductor substrate cleaning method of the present invention. In a more preferred embodiment, the adhesive layer on the semiconductor substrate after separation is cleaned using the semiconductor substrate cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is cleanly removed in a short time using the cleaning method of the present invention. The conditions for this step are as described above.

[0169] As described above, simply by performing a cleaning operation using the cleaning composition of the present invention, the adhesive layer is peeled off or dissolved, and in the fourth step, the adhesive layer on the semiconductor substrate can be removed more cleanly and in a shorter time. Furthermore, as described above, by using the semiconductor substrate cleaning method of the present invention, the electrodes are not damaged when cleaning the semiconductor substrate, particularly when removing the adhesive layer on the semiconductor substrate.

[0170] The method for manufacturing a processed semiconductor substrate of the present invention includes the above-mentioned steps 1 to 4, but may also include steps other than these. Furthermore, the above-mentioned components and methodological elements related to steps 1 to 4 may be variously modified within the scope of the present invention.

[0171] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The following equipment was used: [Equipment] (1) Cleaning equipment: XBC (manufactured by SUSS Microtec)

[0172] [1] Preparation of Cleaning Composition [Preparation Example 1] 24.7 g of N-methyl-2-pyrrolidone (NMP) was added to 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirred to obtain a cleaning composition.

[0173] Preparation Example 2 18.5 g of N-methyl-2-pyrrolidone (NMP) and 6.2 g of dibutyl ether (DBE) were added to 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirred to obtain a cleaning composition.

[0174] Preparation Example 3 13.1 g of N-methyl-2-pyrrolidone (NMP) and 11.6 g of dibutyl ether (DBE) were added to 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirred to obtain a cleaning composition.

[0175] Preparation Example 4 9.88 g of N-ethyl-2-pyrrolidone (NEP), 9.88 g of dibutyl ether (DBE), and 4.94 g of dipropylene glycol dimethyl ether (DPGDM) were added to 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirred to obtain a cleaning composition.

[0176] [2] Value of polar term (δp) (MPa ０．５ The polarity (δp) of the solvents used in the above Preparation Examples was calculated using solubility parameter calculation software (Hansen SP&QSPR model, Winmostar V11, X-Ability Co. Ltd., Japan-Tokyo, 2022), and the results shown in Table 1 below were obtained.

[0177]

[0178] From the results in Table 1 above, the polarity term (δp) values ​​of the cleaning compositions in Preparation Examples 1 to 4 are as shown in Table 2 below. For example, the polarity term (δp) value of the cleaning composition in Preparation Example 2 was calculated by calculating the polarity term (δp) values ​​for each of the NMP solvent and the DBE solvent, taking into account their blending ratios, and then adding them together. Specifically, it was calculated as follows: 9.9 x 0.75 + 3.1 x 0.25 = 8.2 (MPa ０．５ )

[0179]

[0180] [3] Cleaning Test and Confirmation of Bump (Protruding Electrode) Deformation [Example 1] The cleaning composition obtained in Preparation Example 2 was dispensed onto a 4 × 4 cm SiN TEG chip (thickness: 770 μm, bump diameter: 0.03 mm, bump height: 0.04 mm, bump pitch: 0.06 × 0.1 mm) as the device substrate using a cleaning device at a rotation speed of 20 rpm and a supply rate of 100 mL / min for 180 seconds. The substrate surface was then rinsed with isopropyl alcohol and spin-dried to obtain a cleaned substrate. 6,000 bumps on the resulting cleaned substrate were observed using an SEM. A score of ∘ was given if no defects were observed (no bump deformation was observed), and a score of × was given if defects were observed (bump deformation was observed).

[0181] [Examples 2] to [Examples 3] Cleaned substrates were obtained in the same manner as in Example 1, except that the cleaning composition of Preparation Example 2 in Example 1 was changed to the cleaning compositions of Preparation Examples 3 and 4, respectively. The obtained cleaned substrates were evaluated in the same manner as in Example 1.

[0182] A cleaned substrate was obtained in the same manner as in Example 1, except that the cleaning composition of Preparation Example 2 in Example 1 was changed to the cleaning composition of Preparation Example 1. The obtained cleaned substrate was evaluated in the same manner as in Example 1.

[0183] The results of observing the bumps in Examples 1 to 3 and Comparative Example 1 are shown in Table 3 below.

[0184]

[0185] From the results in Table 3, it was confirmed that the cleaning composition according to the present invention does not damage the electrodes when cleaning a semiconductor substrate having electrodes.

Claims

1. A method for cleaning a semiconductor substrate, comprising the step of cleaning a semiconductor substrate having an electrode with a cleaning composition, wherein the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa. ０．５ A method for cleaning a semiconductor substrate, wherein the cleaning temperature is less than 100°C.

2. The method for cleaning a semiconductor substrate according to claim 1, wherein the semiconductor substrate having an electrode is a semiconductor substrate obtained by processing a semiconductor substrate in a laminate including the semiconductor substrate having the electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition, and then separating the support substrate and the semiconductor substrate.

3. The method for cleaning a semiconductor substrate according to claim 2, wherein the adhesive composition contains an adhesive component (S) containing at least one adhesive selected from the group consisting of a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

4. The method for cleaning a semiconductor substrate according to claim 3, wherein the adhesive component (S) includes a siloxane-based adhesive.

5. The method for cleaning a semiconductor substrate according to claim 4, wherein the siloxane adhesive contains a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

6. A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate comprising a semiconductor substrate having an electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of separating the support substrate from the semiconductor substrate; and a fourth step of cleaning the separated semiconductor substrate with a cleaning composition, wherein the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa. ０．５ 10. A method for producing a processed semiconductor substrate, wherein the thickness is less than 100 μm.

7. The method for producing a processed semiconductor substrate according to claim 6, wherein the adhesive composition comprises an adhesive component (S) comprising at least one adhesive selected from the group consisting of a siloxane-based adhesive, an acrylic resin-based adhesive, an epoxy resin-based adhesive, a polyamide-based adhesive, a polystyrene-based adhesive, a polyimide adhesive, and a phenolic resin-based adhesive.

8. The method for producing a processed semiconductor substrate according to claim 7, wherein said adhesive component (S) comprises a siloxane-based adhesive.

9. The method for producing a processed semiconductor substrate according to claim 8, wherein the siloxane-based adhesive comprises a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

10. A cleaning composition used to clean a semiconductor substrate having an electrode, wherein the polar term (δp) in the Hansen solubility parameter (HSP) of the cleaning composition is 9.9 MPa. ０．５ A cleaning composition having a viscosity of less than 1000 MPa.

11. The cleaning composition according to claim 10, wherein the semiconductor substrate having an electrode is a semiconductor substrate obtained by processing a semiconductor substrate in a laminate comprising the semiconductor substrate having the electrode, a support substrate, and an adhesive layer disposed between the semiconductor substrate and the support substrate and obtained from an adhesive composition, and then separating the support substrate and the semiconductor substrate.

12. The cleaning composition according to claim 11, wherein the adhesive composition comprises an adhesive component (S) containing at least one adhesive selected from the group consisting of siloxane-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, and phenolic resin-based adhesives.

13. The cleaning composition of claim 12, wherein the adhesive component (S) comprises a siloxane-based adhesive.

14. The cleaning composition of claim 13, wherein the siloxane adhesive comprises a polyorganosiloxane component (A') that cures via a hydrosilylation reaction.

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