Detergent composition for semiconductor cleaning and method for cleaning semiconductor substrate

Abstract

The invention provides a cleaning agent composition for cleaning a semiconductor. The cleaning agent composition comprises a quaternary ammonium salt and an acid amide compound represented by chemical formula 1. (In the formula, R1 to R3 are organic groups, R1 contains at least one heteroatom, and chemical formula 1 does not contain a cyclic structure in which two or more groups selected from among R1 to R3 are linked. The present invention provides a method for cleaning a semiconductor substrate by applying a cleaning agent composition to a semiconductor substrate in which a temporary adhesive material containing silicone remains on at least one surface, thereby cleaning the semiconductor substrate.

Description

Technical Field

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

[0002] The following is disclosed in Patent Document 1: "A cleaning agent composition for removing a temporary adhesive material containing a silicone compound present on a substrate, characterized in that: The cleaning agent composition contains: (A) Organic solvent: 75 to 99 parts by mass, (B) Water: 0 to 5 parts by mass, and (C) Ammonium salt: 1 to 20 parts by mass (wherein, (A)+(B)+(C)=100 parts by mass), The organic solvent does not contain an organic solvent having a hydroxyl group, and 100 parts by mass of the organic solvent contains 50 parts by mass or more of an organic solvent having a heteroatom, The ammonium salt contains at least one of hydroxide ions, fluoride ions, and chloride ions (Claim 1). " The following is disclosed in Patent Document 2: "A composition containing a fluorinated alkyl quaternary ammonium or a hydrate of a fluorinated alkyl quaternary ammonium and an aprotic solvent, and The aprotic solvent contains: (A) An N-substituted amide compound having 4 or more carbon atoms and no active hydrogen on the nitrogen atom, and (B) An ether compound (Claim 1). " The following is disclosed in Patent Document 3: "A cleaning agent composition for removing adhesive residues, characterized in that: It contains a quaternary ammonium salt and a solvent containing a first organic solvent and a second organic solvent, The first organic solvent is an acid amide derivative represented by formula (Z), The second organic solvent is another organic solvent different from the acid amide derivative, and The water content of this cleaning agent composition is less than 4.0% by mass (Claim 1). " [Background Technical Literature] [Patent Literature] [Patent Document 1] WO2020 / 235605 Gazette [Patent Document 2] WO2020 / 080060 Gazette [Patent Document 3] WO2021 / 100651 Gazette Summary of the Invention [Technical means for solving the problem]

[0003] A first aspect of the present invention provides a cleaning agent composition for semiconductor cleaning, the cleaning agent composition comprising a quaternary ammonium salt and an acid amide compound. The acid amide compound is represented by the following Chemical Formula 1. [Chemical Formula 1] Here, R1 to R3 may be organic groups. R1 may contain at least 1 heteroatom. Chemical Formula 1 may not contain a cyclic structure in which two or more groups selected from R1 to R3 are connected.

[0004] In the said invention, the carbon number of R1 may be 4 or more.

[0005] In the said invention, R1 may contain a -R-O-R' structure, and R and R' may be alkyl groups.

[0006] In the said invention, the carbon number of at least one of R2 and R3 may be 5 or more.

[0007] In the said invention, R2 and R3 may be alkyl groups.

[0008] In the said invention, the quaternary ammonium salt may be represented by R A R B R C R D N + F - Here, R A ~R D may be independently selected from alkyl groups, aryl groups, and aralkyl groups respectively.

[0009] In the said invention, the quaternary ammonium salt may contain a first ammonium salt and a second ammonium salt. The first ammonium salt may be represented by R A R B R C R D N + F - Here, R A ~R D may be independently selected from alkyl groups, aryl groups, and aralkyl groups respectively. The second ammonium salt may be represented by R E R F R G R H N + X - Here, R E ~R H may be independently selected from alkyl groups, aryl groups, and aralkyl groups respectively, and X may be selected from Cl, Br, I, and OH.

[0010] In the present invention, the cleaning composition may contain a first ammonium salt in an amount of 0.1 to 20.0% by mass based on the total amount of the cleaning composition.

[0011] In the present invention, the cleaning composition may contain a second ammonium salt in an amount of 0.1 to 5.0% by mass based on the total amount of the cleaning composition.

[0012] In the present invention, the cleaning composition may further contain a non-polar solvent.

[0013] In the present invention, the non-polar solvent may not contain heteroatoms.

[0014] In the present invention, the cleaning composition may contain an acid amide compound and the non-polar solvent in a total amount of 75.0 to 99.8% by mass based on the total amount of the cleaning composition.

[0015] In the present invention, the cleaning composition may further contain an ether component.

[0016] In the present invention, the cleaning composition may contain an ether component in an amount of 0.1 to 5.0% by mass based on the total amount of the cleaning composition.

[0017] In the present invention, the water content of the cleaning composition may be less than 4.0% by mass.

[0018] In the present invention, the cleaning composition can be used to clean a silicone-containing temporary bonding material remaining on a semiconductor substrate.

[0019] A second aspect of the present invention provides a method for cleaning a semiconductor substrate. The cleaning method can clean the semiconductor substrate by applying a cleaning composition to a semiconductor substrate having a silicone-containing temporary bonding material remaining on at least one surface. The cleaning composition can be the cleaning composition as described above.

[0020] In addition, the above description of the invention does not list all the features required for the present invention. In addition, sub-combinations of these feature groups can also be inventions. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Schematically shows an example of an object 10 to be cleaned by the cleaning composition in the present embodiment. Figure 2 Shows a flow of a method for manufacturing a semiconductor mounting substrate using the cleaning composition of the present embodiment. Figure 3 Shows a semiconductor substrate 110 bonded to a support 130 by a temporary bonding material 150. Figure 4 Shows the semiconductor substrate 110 after thinning the semiconductor substrate 140 before thinning. Figure 5 Indicates the electrode 112 penetrating the semiconductor substrate 110. Figure 6 Indicates an example of a sub-process of the cleaning stage (S500). Figure 7 Indicates an example of the semiconductor mounting substrate 100. DETAILED DESCRIPTION

[0022] The present invention will be described below by way of embodiments of the invention. However, the following embodiments do not limit the invention of the claims. For the solution means of the invention, all combinations of the features described in the embodiments are not necessarily required. In addition, the embodiments will be described with reference to the drawings. However, in the description of the drawings, the same or similar parts may be denoted by the same reference numerals and repeated description may be omitted.

[0023] [Outline of the object to be cleaned 10] Figure 1 Schematically shows an example of the object to be cleaned 10 of the cleaning agent composition in the present embodiment. The object to be cleaned 10 is an object to be cleaned using the cleaning agent composition. The object to be cleaned 10 may be various objects having a silicone-containing adhesive material (hereinafter also referred to as "temporary adhesive material") attached to the surface. The adhesive material on the surface is cleaned using the cleaning agent composition.

[0024] For example, the object to be cleaned 10 may be a semiconductor substrate having a silicone-containing temporary adhesive material remaining on at least one surface. For example, when forming an electrode or the like, the semiconductor substrate may be strengthened by a support, and a silicone-containing temporary adhesive material for bonding the semiconductor substrate to the support may remain. In Figure 1 the example of, the object to be cleaned 10 may include at least a semiconductor substrate 110, an electrode 112, and a temporary adhesive material 120.

[0025] The semiconductor substrate 110 may be a semiconductor substrate having a circuit (not shown) formed on one surface (for example, Figure 1 the upper side). For example, the semiconductor substrate 110 may be a silicon wafer.

[0026] The electrode 112 is an electrode formed on the surface and / or inside of the semiconductor substrate 110. For example, the electrode 112 may be a through-silicon via (TSV) provided so as to penetrate the semiconductor substrate 110. The electrode 112 may include an electrode such as a surface bump provided on the surface of the semiconductor substrate 110.

[0027] The temporary adhesive material 120 is an adhesive material remaining on the surface of the semiconductor substrate 110. The temporary adhesive material 120 may be a material remaining on the circuit surface side of the semiconductor substrate 110. In the manufacturing process of the semiconductor mounting substrate described below, the temporary adhesive material 120 is provided for bonding the semiconductor mounting substrate to the support body, and remains after the support body is peeled off. The semiconductor mounting substrate is completed by cleaning and removing the temporary adhesive material 120 with the cleaning agent composition of the present embodiment.

[0028] [Outline of the cleaning agent composition] The cleaning agent composition of the present embodiment will be described. The cleaning agent composition can be mainly used for semiconductor cleaning applications. In particular, the cleaning agent composition can be used to clean the silicone-containing temporary adhesive material 120 remaining on the semiconductor substrate 110. The cleaning agent composition contains at least (1) a quaternary ammonium salt and (2) an acid amide compound represented by the following Chemical Formula 1. The cleaning agent composition may further contain one or both of (3) a non-polar solvent and (4) an ether component.

[0029] [Regarding (1) Quaternary ammonium salt] The quaternary ammonium salt may contain only the first ammonium salt (one kind). In addition to this, the quaternary ammonium salt may also contain the first ammonium salt and the second ammonium salt (two kinds).

[0030] The first ammonium salt is represented by R A R B R C R D N + F - Here, R A ~R D are each independently selected from an alkyl group, an aryl group, and an aralkyl group.

[0031] The alkyl group may be linear, branched, and / or cyclic with 1 to 20 carbon atoms (preferably 1 to 10). For example, the alkyl group may be: methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, or 2,6-dimethylheptan-4-yl, n-heptyl, 1-methylhexyl, octyl, or n-octyl, etc.

[0032] The aryl group can be monocyclic or polycyclic with 5 to 30 carbon atoms (preferably 6 to 12). For example, the aryl group can be: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, condensed phenyl, fluorenyl. The aryl group can be unsubstituted, or it can also be substituted with an alkyl group or other functional groups.

[0033] The aralkyl group can be an aralkyl group in which the hydrogen of the alkyl group described above is substituted with the aryl group.

[0034] As an example, the first ammonium salt can be: a compound where R A ~R D is methyl, a compound where R A ~R D is ethyl, a compound where R A ~R D is propyl, a compound where R A ~R D is isopropyl, a compound where R A ~R D is n-butyl, a compound where R A ~R D is isobutyl, a compound where R A ~R D is sec-butyl, or a compound where R A ~R D is tert-butyl.

[0035] The first ammonium salt can also be a hydrate. In addition to this, the first ammonium salt can also be an anhydride.

[0036] The cleaning agent composition can contain 0.1 to 20.0% by mass of the first ammonium salt, preferably 1 to 10% by mass, and more preferably 3 to 6% by mass, based on the total amount of the cleaning agent composition.

[0037] By making the cleaning agent composition contain the first ammonium salt, the cleaning power of the cleaning agent composition can be improved. In particular, the first ammonium salt containing fluoride ions helps to dissolve / decompose the silicone-containing temporary adhesive material.

[0038] The second ammonium salt is represented by R E R F R G R H N + X - Here, R E ~R H are each independently selected from an alkyl group, an aryl group, and an aralkyl group. The alkyl group, aryl group, and aralkyl group can be the same as the alkyl group, aryl group, and aralkyl group described in the first ammonium salt. X can be selected from Cl, Br, I, and OH. X can preferably be Cl, Br, or I.

[0039] The secondary ammonium salt can also be a hydrate. In addition to this, the secondary ammonium salt can also be an anhydride.

[0040] The cleaning composition may contain 0.1 to 5.0% by mass, preferably 1 to 4% by mass, of the secondary ammonium salt based on the whole cleaning composition.

[0041] The secondary ammonium salt can enhance the cleaning ability of the primary ammonium salt and reduce the polarity of the cleaning composition. By including the secondary ammonium salt in the cleaning composition, compared with the case where only the primary ammonium salt is included, the polarity of the cleaning composition can be inhibited, making it easier for the cleaning composition to penetrate into the silicone-containing temporary adhesive material and making the decomposition products easily dissolve in the cleaning composition.

[0042] In addition to the primary ammonium salt and the secondary ammonium salt, the quaternary ammonium salt may also contain other ammonium salts.

[0043] [Regarding (2) the acid amide compound represented by Chemical Formula 1] The acid amide compound is represented by the following Chemical Formula 1. [Chemical Formula 1] [Chemical Formula 2]

[0044] In Chemical Formula 1, R1 to R3 are organic groups. Chemical Formula 1 does not contain a cyclic structure in which two or more groups selected from R1 to R3 are connected. For example, Chemical Formula 1 does not contain a cyclic structure in which R1 and R2 are bonded, a cyclic structure in which R2 and R3 are bonded, a cyclic structure in which R1 and R3 are bonded, or a cyclic structure in which R1 to R3 are bonded.

[0045] This acid amide compound increases the polarity of the cleaning composition. In the case where the cleaning composition does not contain the acid amide compound, there are concerns that the polarities of the quaternary ammonium salt (especially the primary ammonium salt) and other components deviate from each other too much, resulting in phase separation, or the penetration of the cleaning composition into the temporary adhesive material stagnates. If a cyclic structure in which R1 to R3 are connected is adopted, there is a concern that the permeability of the cleaning composition to the temporary adhesive material decreases, but according to this embodiment, by excluding such a cyclic structure, the permeability of the cleaning composition to the temporary adhesive material can be increased. Furthermore, by including the acid amide compound, the decomposition products can be easily dissolved in the cleaning composition.

[0046] R1 is an organic group containing at least one heteroatom. For example, the heteroatom can be O, N, or S. As an example, R1 can contain an -R-O-R' structure, where R and R' can be alkyl groups. R and R' can be straight-chain, branched-chain, and / or cyclic alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). The total number of carbon atoms of R and R' can be 3 or more. That is, the number of carbon atoms of R1 can be 3 or more. By adopting this concept for the acid amide compound, an appropriate polarity can be maintained.

[0047] For example, R and R' can be independently selected from the following groups: methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, or 2,6-dimethylheptan-4-yl, n-heptyl, 1-methylhexyl, octyl, or n-octyl, etc.

[0048] R and R' can have the same structure. Or, R and R' can have different structures. Additionally, although strictly speaking R is a divalent alkylene group, R can have a structure obtained by removing a hydrogen atom from the alkyl groups exemplified above.

[0049] R2 and R3 are alkyl groups. R2 and R3 can be straight-chain, branched-chain, and / or cyclic alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). For example, the number of carbon atoms of at least one of R2 and R3 can be 1 or more, 3 or more, or 5 or more.

[0050] R2 and R3 can be selected from the following groups: methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, or 2,6-dimethylheptan-4-yl, n-heptyl, 1-methylhexyl, octyl, n-octyl, etc.

[0051] As a specific example, the acid amide compound can be: 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-pentyloxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropanamide, 3-methoxy-N,N-diethylpropanamide, 3-ethoxy-N,N-diethylpropanamide, 3-propoxy-N,N-diethylpropanamide, 3-butoxy-N,N-diethylpropanamide, 3-pentyloxy-N,N-diethylpropanamide, 3-hexyloxy-N,N-diethylpropanamide, 3-methoxy-N,N-dipropylpropanamide, 3-ethoxy-N,N-dipropylpropanamide, 3-propoxy-N,N-dipropylpropanamide, 3-butoxy-N,N-dipropylpropanamide, 3-pentyloxy-N,N-dipropylpropanamide, 3-hexyloxy-N,N-dipropylpropanamide, 3-methoxy-N,N-dibutylpropanamide, 3-ethoxy-N,N-dibutylpropanamide, 3-propoxy-N,N-dibutylpropanamide, 3-butoxy-N,N-dibutylpropanamide, 3-pentyloxy-N,N-dibutylpropanamide, 3-hexyloxy-N,N-dibutylpropanamide, 3-methoxy-N,N-dipentylpropanamide, 3-ethoxy-N,N-dipentylpropanamide, 3-propoxy-N,N-dipentylpropanamide, 3-butoxy-N,N-dipentylpropanamide, 3-pentyloxy-N,N-dipentylpropanamide, 3-hexyloxy-N,N-dipentylpropanamide, 4-methoxy-N,N-dimethylbutanamide, 4-ethoxy-N,N-dimethylbutanamide, 4-propoxy-N,N-dimethylbutanamide, 4-butoxy-N,N-dimethylbutanamide, 4-pentyloxy-N,N-dimethylbutanamide, 4-hexyloxy-N,N-dimethylbutanamide, 4-methoxy-N,N-diethylbutanamide, 4-ethoxy-N,N-diethylbutanamide, 4-propoxy-N,N-diethylbutanamide, 4-butoxy-N,N-diethylbutanamide, 4-pentyloxy-N,N-diethylbutanamide, 4-hexyloxy-N,N-diethylbutanamide, 4-methoxy-N,N-dipropylbutanamide, 4-ethoxy-N,N-dipropylbutanamide, 4-propoxy-N,N-dipropylbutanamide, 4-butoxy-N,N-dipropylbutanamide, 4-pentyloxy-N,N-dipropylbutanamide, 4-hexyloxy-N,N-dipropylbutanamide, 4-methoxy-N,N-dibutylbutanamide, 4-ethoxy-N,N-dibutylbutanamide, 4-propoxy-N,N-dibutylbutanamide, 4-butoxy-N,N-dibutylbutanamide, 4-pentyloxy-N,N-dibutylbutanamide, 4-hexyloxy-N,N-dibutylbutanamide, 4-methoxy-N,N-dipentylbutanamide, 4-ethoxy-N,N-dipentylbutanamide, 4-propoxy-N,N-dipentylbutanamide, 4-butoxy-N,N-dipentylbutyramide, 4-pentyloxy-N,N-dipentylbutyramide, or 4-hexyloxy-N,N-dipentylbutyramide.,

[0052] The cleaning composition may contain 10 to 99.8% by mass, preferably 30 to 99% by mass, of the acid amide compound represented by Chemical Formula 1 in the overall cleaning composition.

[0053] [Regarding (3) non-polar solvent] The non-polar solvent is an organic solvent with no polarity or very low polarity. The non-polar solvent may be selected from non-polar solvents well-known as non-polar solvents in general. The non-polar solvent may not contain heteroatoms. The non-polar solvent may be an unsubstituted alkane, alkene, or aryl. As an example, the non-polar solvent may be a saturated aliphatic hydrocarbon, unsaturated aliphatic hydrocarbon, saturated alicyclic hydrocarbon, unsaturated alicyclic hydrocarbon, terpene compound, and / or terpene compound.

[0054] As an example, the saturated aliphatic hydrocarbon may be: n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, undecane, dodecane, or tridecane, etc.

[0055] As an example, the unsaturated aliphatic hydrocarbon may be: 1-octene, 1-nonene, 1-decene, 1-dodecene, or β-myrcene, etc.

[0056] As an example, the saturated alicyclic hydrocarbon may be: cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, or decalin, etc.

[0057] As an example, the unsaturated alicyclic hydrocarbon may be cyclohexene, etc.

[0058] As an example, the terpene compound may be: p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpin, 1,8-terpin, camphane, norcamphane, pinane, thujane, carane, longifolene, geraniol, neral, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, or dipentene, etc.

[0059] As an example, the aromatic hydrocarbon may be: benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, or tetralin, etc.

[0060] The cleaning agent composition may contain 0 to 90% by mass, preferably 10 to 50% by mass, of (3) non-polar solvent based on the total cleaning agent composition. The cleaning agent composition may contain a total of 75.0 to 99.8% by mass of (2) acid amide compound and (3) non-polar solvent based on the total cleaning agent composition.

[0061] [Regarding (4) ether component] The ether component may be: alkyl ether, glycol ether, or aryl ether. As the ether component, a single component may be used, or a mixture of multiple components may be used.

[0062] The alkyl ether may be an ether containing an alkyl group. For example, it may be: diethyl ether, di-n-propyl ether, di-n-butyl ether, di-n-pentyl ether, di-n-hexyl ether, or tert-butyl methyl ether.

[0063] The glycol ether may be an ether having a hydroxyl group. For example, it may be: aryl ether compounds such as anisole, diphenyl ether, bis(2-methoxyethyl) ether, bis(2-ethoxyethyl) ether, bis(2-butoxyethyl) ether, or pentaethylene glycol monododecyl ether.

[0064] The aryl ether may be an ether having an aryl group. For example, it may be: ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, or diphenyl ether.

[0065] The ether can adjust the polarity of the cleaning agent composition. By including an ether in the cleaning agent composition, a certain degree of polarity is imparted to the cleaning agent composition, preventing phase separation between the quaternary ammonium salt (especially the primary ammonium salt) and the non-polar solvent in the cleaning agent composition, and facilitating the penetration of the quaternary ammonium salt (especially the primary ammonium salt) into the temporary adhesive material.

[0066] The cleaning agent composition may contain 0.1 to 5.0% by mass, preferably 1.0 to 4.0% by mass, of (4) ether component based on the total cleaning agent composition. [Other components] The cleaning agent composition may also contain components other than the aforementioned (1) to (4). For example, the cleaning agent composition may contain water as needed. Here, the water content of the cleaning agent composition is preferably less than 4.0% by mass. In addition, the cleaning agent composition may contain various additives as needed, such as: surfactants, chelating agents, antioxidants, rust inhibitors, defoamers, pH adjusters, etc.

[0067] The preparation method of the cleaning agent composition is not particularly limited. The cleaning agent composition can be manufactured by mixing the aforementioned components. The mixing order is not particularly limited. The flash point of the cleaning agent composition may be 21°C or higher. If the flash point is within the aforementioned range, then the object to be cleaned can be safely cleaned.

[0068] [Outline of the method for manufacturing a semiconductor mounting substrate] Here, a method for manufacturing a semiconductor mounting substrate using the cleaning agent composition of the present embodiment will be described.

[0069] Figure 2 The flowchart showing the method for manufacturing a semiconductor mounting substrate using the cleaning agent composition of the present embodiment is shown. For example, by performing each of the processes of S100 to S500, a semiconductor mounting substrate can be manufactured. Part of S100 to S500 may be omitted. Other processes may also be performed as needed in addition to performing S100 to S500.

[0070] First, in S100, a bonding step is performed, and the circuit surface of a semiconductor substrate having a circuit formed on one surface is bonded to a support using a silicone-containing temporary bonding material. Figure 3 FIG. shows a semiconductor substrate 140 before thinning that is bonded to a support 130 using a silicone-containing temporary bonding material 150.

[0071] The semiconductor substrate 140 before thinning is a semiconductor substrate having a circuit formed on one surface. For example, the semiconductor substrate 140 before thinning may be a semiconductor wafer having a semiconductor circuit formed on one surface. The semiconductor wafer may be selected from a silicon wafer, a germanium wafer, a gallium-arsenide wafer, a gallium-phosphorus wafer, and a gallium-arsenide-aluminum wafer.

[0072] The temporary bonding material 150 is a bonding material containing cured silicone. The temporary bonding material 150 before curing (hereinafter also referred to as "uncured composition") may contain a thermosetting organopolysiloxane and / or a thermoplastic organopolysiloxane.

[0073] The temporary bonding material 150 preferably contains: a siloxane unit (M unit) represented by R 1 R 2 R 3 SiO 1 / 2 in an amount of 0.001 mol% or more and 60.000 mol% or less, a siloxane unit (D unit) represented by R 4 R 5 SiO 2 / 2 in an amount of 10.000 mol% or more and 99.999 mol% or less, a siloxane unit (T unit) represented by R 6 SiO 3 / 2 in an amount of 0.000 mol% or more and 0.005 mol% or less, and a siloxane unit (SiO 4 / 2The siloxane units (Q units) represented. In addition, the temporary adhesive material 150 is more preferably composed of: M units in an amount of 0.001 mol% or more and 35.000 mol% or less, D units in an amount of 30.000 mol% or more and 99.999 mol% or less, T units in an amount of 0.000 mol% or more and 0.001 mol% or less, and Q units in an amount of 0.000 mol% or more and 50.000 mol% or less.

[0074] Here, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are organic substituents and are unsubstituted or substituted monovalent hydrocarbon groups. In this hydrocarbon group, the number of carbon atoms is preferably 1 to 10. Specific examples of the hydrocarbon group include: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, cyclopentyl, and n-hexyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl; groups in which part or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms. Among these, methyl and phenyl are preferred.

[0075] The uncured composition may contain, for example: (A-1) an organopolysiloxane having two or more alkenyl groups in one molecule, (A-2) an organohydrogenpolysiloxane containing two or more hydrogen atoms bonded to silicon atoms (Si-H groups) in one molecule, and (A-3) a platinum-based catalyst. Here, the molar ratio of the Si-H groups in component (A-2) to the alkenyl groups in component (A-1) is 0.3 or more and 10 or less. In addition, the uncured composition may also contain (A-4) an organic solvent or (A-5) a reaction control agent.

[0076] Component (A-1) is an organopolysiloxane having two or more alkenyl groups in one molecule. Component (A-1) is, for example, a linear or branched diorganopolysiloxane containing two or more alkenyl groups in one molecule, or an organopolysiloxane having a resin structure with siloxane units (Q units) represented by SiO4 / 2 units. Component (A-1) is preferably an organopolysiloxane having 0.6 mol% or more and 9 mol% or less (molar ratio of alkenyl groups / Si moles) of alkenyl groups in one molecule.

[0077] Specifically, such organopolysiloxanes are represented by the following formulas (1), (2), and (3). These organopolysiloxanes may be used alone or two or more of them may be used simultaneously. R 7 (3-a) Z a SiO-(R 7 ZSiO) m -(R 72SiO n -SiR 7 (3-a) Z a (1) R 7 2(HO)SiO-(R 7 ZSiO) p+2 -(R 7 2SiO) q -SiR 7 2(OH) (2) (SiO 4 / 2 ) b (R 7 3SiO 1 / 2 ) c (R 7 (3-e) Z e SiO 1 / 2 ) d (3)

[0078] In the formula, R 7 are each independently a monovalent hydrocarbon group having no aliphatic unsaturated bond, Z are each independently a monovalent organic group containing an alkenyl group, a is an integer of 0 to 3, m and n are numbers such that 2a + m makes the alkenyl content in 1 molecule become 0.6 mol% or more and 9 mol% or less. p and q are numbers such that p + 2 makes the alkenyl content in 1 molecule become 0.6 mol% or more and 9 mol% or less. e are each independently an integer of 1 to 3, and b, c, and d are numbers such that (c + d) / b is 0.3 to 3.0 and d / (b + c + d) is 0.01 to 0.6.

[0079] In the formula, as R 7 , it is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. As R 7 , specifically, examples include: alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl. Among these, alkyl groups or phenyl groups are preferred.

[0080] As Z, it is preferably an organic group having 2 to 10 carbon atoms. Examples of Z include: alkenyl groups such as vinyl, allyl, hexenyl, and octenyl; (meth)acryloylalkyl groups such as acryloylpropyl, acryloylmethyl, methacryloylpropyl; (meth)acryloyloxyalkyl groups such as acryloyloxypropyl, acryloyloxymethyl, methacryloyloxypropyl, and methacryloyloxymethyl; cyclohexenylethyl, vinyloxypropyl, etc. Among these, vinyl is preferably used industrially.

[0081] In the formula (1), as long as a is 1 to 3, the molecular chain end is capped with an alkenyl group. Since the alkenyl group at the molecular chain end with good reactivity can complete the reaction in a short time, it is preferred. Further, from the industrial or cost aspect, a = 1 is preferred. The property of the diorganopolysiloxane containing the alkenyl group is preferably oily or raw rubber-like.

[0082] The formula (3) represents an organopolysiloxane having a resin structure. In the formula (3), from the industrial or cost aspect, e = 1 is preferred. In addition, the product of the average value of e and d / (b + c + d) is preferably 0.02 to 1.50, more preferably 0.03 to 1.0. The organopolysiloxane having a resin structure can also be dissolved in an organic solvent and used in the form of a solution.

[0083] Component (A-2) is a crosslinking agent and is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule. The organohydrogenpolysiloxane is linear, branched or cyclic. For example, an organohydrogenpolysiloxane having at least 2, more preferably 2 or more and 100 or less, further preferably 3 or more and 50 or less hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule and being linear, branched or cyclic can be used.

[0084] The viscosity of component (A-2) at 25°C is preferably 1 mPa·s or more and 5,000 mPa·s or less, more preferably 5 mPa·s or more and 500 mPa·s or less. The organohydrogenpolysiloxane can be used alone or two or more kinds can be used simultaneously.

[0085] Component (A-2) is preferably formulated in the following amount so that the molar ratio (Si-H group / alkenyl group) of the Si-H group in component (A-2) to the alkenyl group in component (A-1) is preferably 0.3 or more and 10 or less, more preferably 1.0 or more and 8.0 or less. As long as the molar ratio is 0.3 or more, the crosslinking density will not become too low, and the uncured composition layer can be suitably cured. As long as the molar ratio is 10 or less, the crosslinking density will not become too high, and sufficient adhesion and tackiness can be obtained. In addition, as long as the molar ratio is 10 or less, the pot life of the uncured composition can also be extended.

[0086] Component (A-3) is a platinum-based catalyst (that is, a platinum group metal catalyst). Examples of the platinum-based catalyst include: chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol, a reaction product of chloroplatinic acid and an olefin compound, a reaction product of chloroplatinic acid and a vinyl-containing siloxane, etc. The platinum-based catalyst can be used alone or two or more kinds can be used simultaneously. Component (A-3) is preferably formulated in the following amounts such that, relative to the total of components (A-1) and (A-2), the platinum group metal component (in terms of mass) is preferably 1 ppm or more and 5,000 ppm or less, more preferably 5 ppm or more and 2,000 ppm or less. As long as the content is 1 ppm or more, the curability of the uncured composition layer is less likely to decrease. Therefore, not only can the crosslink density be inhibited from decreasing, but also the holding force can be inhibited from decreasing. As long as the content is 5,000 ppm or less, the pot life of the uncured composition can be extended.

[0087] Component (A-4) is an organic solvent. There is no particular limitation on the organic solvent as long as it can dissolve the components of the uncured composition. Examples of the organic solvent include hydrocarbon solvents such as pentane, hexane, cyclohexane, isooctane, nonane, decane, p-menthane, pinene, isododecane, and limonene; and silicone solvents. The organic solvent can be used alone or two or more kinds can be used simultaneously.

[0088] When using component (A-4), component (A-4) is preferably formulated in the following amounts such that, relative to 100 parts by mass of the total of components (A-1) and (A-2), it is preferably 10 parts by mass or more and 900 parts by mass or less, more preferably 25 parts by mass or more and 400 parts by mass or less, and further preferably 40 parts by mass or more and 300 parts by mass or less.

[0089] Component (A-5) is a reaction control agent. By means of the reaction control agent, when formulating the uncured composition or when coating the uncured composition on a substrate, thickening or gelation of the uncured composition before heat curing can be inhibited.

[0090] Examples of the reaction control agent include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3-methyl-3-trimethylsilanyloxy-1-butyne, 3-methyl-3-trimethylsilanyloxy-1-pentyne, 3,5-dimethyl-3-trimethylsilanyloxy-1-hexyne, 1-ethynyl-1-trimethylsilanyloxycyclohexane, bis(2,2-dimethyl-3-butynyloxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, etc. Among these, 1-ethynylcyclohexanol and 3-methyl-1-butyn-3-ol are preferred. The reaction control agent can be used alone or two or more kinds can be used simultaneously.

[0091] When using the component (A-5), it is preferably formulated in the following amounts such that, relative to 100 parts by mass in total of the components (A-1) and (A-2), it is preferably 0.01 part by mass or more and 8.0 parts by mass or less, more preferably 0.05 part by mass or more and 2.0 parts by mass or less. As long as the content is 8.0 parts by mass or less, the curability of the uncured composition layer is less likely to decrease. As long as the content is 0.01 part by mass or more, the effect of controlling the reaction can be fully exhibited.

[0092] In addition, the uncured composition may further contain other components. Examples of other components include: fillers such as silica; non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane; antioxidants such as phenolic, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based, and thioether-based antioxidants; light stabilizers such as triazole-based and benzophenone-based light stabilizers; flame retardants such as phosphate-based, halogen-based, phosphorus-based, and antimony-based flame retardants; antistatic agents such as cationic surfactants, anionic surfactants, and nonionic surfactants, etc. The other components may be used individually as 1 type, or 2 or more types may be used simultaneously. The other components are formulated within the range that does not impair the object of the present invention. For example, in the case of using a filler to improve heat resistance, the filler is preferably formulated in the following amount such that it is 50 parts by mass or less relative to 100 parts by mass in total of (A-1) and the component (A-2).

[0093] The support 130 may be a plate that can withstand high temperatures and the like and has sufficient strength. For example, the support 130 may be a silicon wafer, a glass plate, or a quartz wafer. A release layer may also be formed in advance on the surface of the support 130 to facilitate the separation of the temporary adhesive material.

[0094] Bonding can be performed by the following method: coating the uncured composition on the support 130 and drying it, and then laminating the semiconductor substrate 140 before thinning on the uncured composition and then thermally curing it. Coating of the uncured composition can be carried out by spin coating, slit coating, or spraying. Depending on the volatilization conditions of the solvent contained in the uncured composition, drying can be performed at a temperature of 80°C or higher and 250°C or lower, preferably 100°C or higher and 230°C or lower. Instead of coating and drying the uncured composition, a film of the pre-cured or semi-cured uncured composition may also be sandwiched between the support 130 and the semiconductor substrate 140 before thinning.

[0095] The bonding can be carried out under reduced pressure and / or increased pressure conditions, and can also be further carried out under heating conditions (for example, 40 to 250 °C) as required. The bonding can be carried out using commercially available wafer bonding devices (for example, EVG520IS, 850TB (trade name) manufactured by EVG, XBC300 (trade name) manufactured by SUSS, SynapseV (trade name) manufactured by Tokyo Electron Limited).

[0096] The thermosetting can be carried out under conditions that sufficiently harden the uncured composition. For example, the thermosetting can be carried out at a temperature of 120 °C or higher and 250 °C or lower, preferably 140 °C or higher and 200 °C or lower, for 10 minutes or longer and 4 hours or shorter, preferably 30 minutes or longer and 2 hours or shorter.

[0097] Next, in S200, a thinning stage is performed to thin the opposite surface of the circuit surface (the surface on the side of the support 130) of the semiconductor substrate 140 before thinning. After the thinning stage, as Figure 4 shown, the semiconductor substrate 140 before thinning becomes the semiconductor substrate 110 after thinning.

[0098] The thinning can be performed by cutting and / or grinding. The thinning can be performed by making the thickness of the semiconductor substrate 110, for example, 5 μm or more and 300 μm or less, preferably 10 μm or more and 100 μm or less. The method of cutting and / or grinding is not particularly limited, and a known method can be used. For example, grinding can be performed while watering the substrate and the grindstone (such as diamond) to cool them. For example, CMP grinding can also be performed on the back surface of the substrate. In addition, for example, a known grinding and cutting device (such as DAG-810 (trade name) manufactured by DISCO Corporation) can be used for cutting.

[0099] Next, in S300, an electrode formation stage is performed to form an electrode on the opposite surface of the circuit surface of the semiconductor substrate 110. As Figure 5 shown, an electrode 112 penetrating the semiconductor substrate 110 is formed.

[0100] For example, a through-silicon via (TSV) can also be provided as the electrode 112. A surface electrode can also be formed on the surface of the semiconductor substrate 110 (the surface opposite to the temporary adhesive material 150) as the electrode 112.

[0101] In S300, various processes can be performed on the surface of the semiconductor substrate 110 (the surface opposite to the temporary bonding material 150). For example, in addition to forming electrodes, metal circuit formation, protective film formation, and / or dicing, etc. can be performed. During these processing steps, required processes such as metal sputtering, wet / dry etching, photolithography, and / or surface oxidation treatment of semiconductors such as silicon can be executed.

[0102] Next, in S400, a peeling step is performed to peel the semiconductor substrate 110 from the support 130. By performing the peeling step, the support 130 is separated from the semiconductor substrate 110.

[0103] The peeling step can be performed in a low-temperature environment from room temperature to about 60°C. The peeling step can be performed by a pull-up method, a peeling method, or a solvent peeling method. The pull-up method can be performed as follows: After fixing one of the semiconductor substrate 110 or the support 130 in the horizontal direction in advance, the other is pulled up at a certain angle with respect to the horizontal direction.

[0104] The peeling method can be performed as follows: A dicing tape is adhered to the surface of the semiconductor substrate 110 (the surface opposite to the temporary bonding material 150). After the dicing tape surface is vacuum adsorbed to the adsorption surface, the support 130 is peeled off from the semiconductor substrate 110 (peel off).

[0105] In the solvent peeling method, the semiconductor substrate 110 and the support 130 can be peeled while dissolving at least a part of the temporary bonding material 150 with a solvent. The solvent can be any material that can dissolve the temporary bonding material 150. For example, organic solvents such as hydrocarbon-based, aromatic-based, and ether-based with 4 to 20 carbon atoms can be used, or the cleaning agent composition of the present embodiment can also be used.

[0106] After the support 130 is peeled off by peeling, at least a part of the temporary bonding material 150 remains on the surface of the semiconductor substrate 110 in the form of the temporary bonding material 120. This state is the same as that shown in Figure 1 and it becomes the cleaning object 10 in the subsequent cleaning step.

[0107] Next, in S500, a cleaning step is performed to clean the peeled semiconductor substrate 110 using the cleaning agent composition. That is, the semiconductor substrate 110 is cleaned by applying the cleaning agent composition to the semiconductor substrate 110 with the silicone-containing temporary bonding material remaining on at least one surface. Hereinafter, the cleaning method performed in the cleaning step will be described in more detail.

[0108] [Summary of the cleaning method for a semiconductor substrate] Figure 6 This is an example of a sub - process representing the cleaning stage (S500). The cleaning method (S500) of the semiconductor substrate 110 can be carried out by executing a part or all of S510 - S550.

[0109] First, in S510, the semiconductor substrate 110 is immersed in a cleaning agent composition. The immersion can be carried out for 10 seconds to 30 minutes, preferably 30 seconds to 10 minutes. Ultrasonic waves can also be applied during the immersion for ultrasonic cleaning. Instead of / in addition to immersion, the cleaning agent composition can be sprayed onto the semiconductor substrate 110 in a mist form, and / or the semiconductor substrate 110 can be cleaned using a paddle with the cleaning agent composition. The cleaning temperature can be 10 - 50 °C, preferably 20 - 40 °C.

[0110] In S530, the cleaned semiconductor substrate 110 is rinsed. For example, the semiconductor substrate 110 is cleaned with a rinsing liquid to remove the cleaning agent composition. The rinsing liquid can be water or alcohol, for example, isopropyl alcohol.

[0111] In S550, the rinsed semiconductor substrate 110 is dried. As long as it is dried under conditions that allow the rinsing liquid to dry sufficiently, for example, it can be dried at a temperature of 30 - 100 °C for 1 - 10 minutes.

[0112] In this way, by executing each stage of S100 - S500, it is possible to manufacture Figure 7 the semiconductor - mounted substrate 100 as shown, in which the temporary bonding material 120 on the surface of the semiconductor substrate 110 has been sufficiently removed. In particular, according to this embodiment, by keeping the polarity of the cleaning agent composition within an appropriate range, the penetration power of the cleaning agent composition into the silicone - containing temporary bonding material can be improved, enabling the cleaning power of the quaternary ammonium salt (especially the first ammonium salt) to take effect and strongly cleaning and removing the silicone - containing temporary bonding material. Thus, a semiconductor - mounted substrate 100 with no remaining temporary bonding material 120 or very little remaining bonding material can be obtained.

[0113] [Examples] Hereinafter, examples are shown, but this embodiment is not limited to the examples.

[0114] (Preparation Example 1) The following raw materials are mixed to obtain cleaning agent composition 1. (1 - 1) Tetrabutylammonium fluoride (TBAF) trihydrate 4.7 mass% (1 - 2) Quaternary ammonium salt represented by the following chemical formula A 0.3 mass% (2) 95% by mass of 3-butoxy-N,N-dimethylpropanamide [Chemical Formula A] [Chemical Formula 3]

[0115] The following method can be used for mixing. First, add the quaternary ammonium salt of (1-1) to the acid amide compound of (2), and stir well to dissolve it. Next, after adding the quaternary ammonium salt of (1-2), stir well to dissolve it.

[0116] (Preparation Example 2) Mix the following raw materials to obtain Detergent Composition 2. Mix according to the same procedure as Detergent Composition 1. (1-1) 4.5% by mass of tetrabutylammonium fluoride (TBAF) trihydrate (1-2) 0.5% by mass of the quaternary ammonium salt represented by Chemical Formula A (2) 95% by mass of 3-methoxy-N,N-dimethylpropanamide

[0117] (Preparation Example 3) Mix the following raw materials to obtain Detergent Composition 3. Mix according to the same procedure as Detergent Composition 1. (1-1) 4.7% by mass of tetrabutylammonium fluoride (TBAF) trihydrate (1-2) 0.3% by mass of the quaternary ammonium salt represented by Chemical Formula A (2) 95% by mass of 3-methoxy-N,N-dimethylpropanamide

[0118] (Preparation Example 4) Mix the following raw materials to obtain Detergent Composition 4. After mixing according to the same procedure as Detergent Composition 1, add the non-polar solvent of (3), and stir well to dissolve it. (1-1) 4.7% by mass of tetrabutylammonium fluoride (TBAF) trihydrate (1-2) 0.3% by mass of the quaternary ammonium salt represented by Chemical Formula A (2) 47.5% by mass of 3-butoxy-N,N-dimethylpropanamide (3) 47.5% by mass of p-menthane

[0119] (Preparation Example 5) Mix the following raw materials to obtain Detergent Composition 5. Mix according to the same procedure as Detergent Composition 4. (1-1) 4.7% by mass of tetrabutylammonium fluoride (TBAF) trihydrate (1-2) 0.3 mass % of the quaternary ammonium salt represented by chemical formula A (2) 47.5 mass % of 3-butoxy-N,N-dimethylpropanamide (3) 47.5 mass % of ethylcyclohexane

[0120] (Preparation Example 6) The following raw materials were mixed to obtain Detergent Composition 6. (1-1) 4.7 mass % of tetrabutylammonium fluoride (TBAF) trihydrate (2) 95 mass % of 3-butoxy-N,N-dimethylpropanamide (4) 0.3 mass % of pentaethylene glycol monododecyl ether

[0121] Mixing was carried out by the following method. First, the quaternary ammonium salt of (1-1) was added to the acid amide compound of (2) and stirred well to dissolve it. Next, after adding the ether component of (4), it was stirred well to dissolve it.

[0122] (Preparation Example 7) The following raw materials were mixed to obtain Detergent Composition 7. (1-1) 4.7 mass % of tetrabutylammonium fluoride (TBAF) trihydrate (1-2) 0.3 mass % of the quaternary ammonium salt represented by chemical formula A (9) 95 mass % of N,N-dimethyloctanamide

[0123] Mixing was carried out by the following method. First, the quaternary ammonium salt of (1-1) was added to N,N-dimethyloctanamide of (9) and stirred well to dissolve it. Next, after adding the quaternary ammonium salt of (1-2), it was stirred well to dissolve it.

[0124] [Example 1] An uncured composition was prepared as follows. 3.5 parts (2 moles relative to alkenyl) of an organohydrogenpolysiloxane represented by the following formula (M-1) and 0.7 part of ethynylcyclohexanol were added to and mixed with the following solution containing 100 mass parts of polydimethylsiloxane and 400 mass parts of isododecane. The polydimethylsiloxane has 2.0 mol% vinyl groups at both ends and side chains, the molecular ends are capped with SiMe2Vi groups, and the number average molecular weight (Mn) obtained by GPC is 50,000. Further, 0.5 part of a platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and filtration was carried out using a 0.2 μm membrane filter to obtain an uncured composition.

[0125] Prepare a 200 mm glass wafer (thickness: 700 μm) as a support. After spin-coating the uncured composition on the support, it is heated on a hot plate at 100 °C for 5 minutes to form a temporary adhesive material layer (thickness: 35 μm). Next, a 200 mm diameter silicon wafer (thickness: 725 μm) is bonded to the support as a semiconductor substrate. Bonding is performed using a wafer bonding apparatus (manufactured by EVG Corporation, EVG520IS (trade name)). In addition, it is carried out under the conditions of a bonding temperature of 50 °C, a chamber pressure during bonding of 10-3 mbar or less, and a load of 10 kN. After bonding, the completed bonded semiconductor substrate is heated in an oven at 200 °C for 2 hours to harden the temporary adhesive material and then cooled to room temperature.

[0126] Next, the back surface of the semiconductor substrate (the opposite side to the support side) is ground. Specifically, the silicon wafer is back-ground using a diamond grinding stone with a grinder (manufactured by DISCO Corporation, DAG810 (trade name)). Grinding is performed until the final substrate thickness reaches 50 μm.

[0127] Next, as a process equivalent to processing, a heating step is simulated on the back surface of the semiconductor substrate. Specifically, the back-ground semiconductor substrate is heated on a hot plate at 260 °C for 10 minutes.

[0128] The support is peeled off from the semiconductor substrate. Specifically, a cutting tape is pasted on the back surface (the side where no circuit is formed) of the silicon wafer using a cutting frame, and the cutting tape surface is set on an adsorption plate by vacuum adsorption. Thereafter, at room temperature, one part of the glass wafer is pulled up with tweezers to peel the glass wafer from the temporary adhesive material.

[0129] Next, the surface of the semiconductor substrate (the peeled side) is cleaned using cleaning agent composition 1. Specifically, the silicon wafer is immersed in cleaning agent composition 1 at room temperature for 5 minutes, then rinsed with isopropyl alcohol and air-dried.

[0130] [Example 2] The same steps as in Example 1 are performed using cleaning agent composition 2 instead of cleaning agent composition 1.

[0131] [Example 3] The same steps as in Example 1 are performed using cleaning agent composition 3 instead of cleaning agent composition 1.

[0132] [Example 4] The same steps as in Example 1 are performed using cleaning agent composition 4 instead of cleaning agent composition 1.

[0133] [Example 5] Perform the same steps as in Example 1 using cleaning composition 5 in place of cleaning composition 1.

[0134] [Example 6] Perform the same steps as in Example 1 using cleaning composition 6 in place of cleaning composition 1.

[0135] [Comparative Example] Perform the same steps as in Example 1 using cleaning composition 7 in place of cleaning composition 1.

[0136] [Analysis and Evaluation] Analyze and evaluate the cleaning performed in the examples. The cleaned semiconductor substrates of each example were analyzed using X-ray photoelectron spectroscopy (XPS), and the elemental distribution on the surface was analyzed. The measuring apparatus used was PHI Quantera SXM manufactured by ULVAC-PHI, Inc. The X-ray source used was monochromatic Al Kα, and the analysis was performed under the conditions of a power of 25 W (15 kV, 100 μm diameter), a photoelectron grazing angle of 45°, a pass energy of 55.0 eV, and a step resolution of 0.05 eV.

[0137] The Si content rates in each example are shown in the following table. The Si content rates in the table do not include Si from the silicon substrate. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 2％ 2％ 2％ 3％ 1％ 2％ 24％

[0138] As shown in Table 1, in Examples 1 to 6 that satisfy the conditions of the present invention, for the silicone-containing temporary adhesive material remaining on the substrate, good cleanability can be obtained in a short time. Therefore, subsequent semiconductor processing steps can be carried out well. On the other hand, in the comparative example where the acid amide compound does not have a heteroatom, it can be seen that more Si remains and the cleanability is poor. The substrates cleaned in the comparative example cannot be used for subsequent semiconductor processing steps.

[0139] The present invention has been described above using embodiments, but the technical scope of the present invention is not limited to the scope described in the above embodiments. It should be understood by those skilled in the art that various modifications or improvements can be added to the above embodiments. In addition, within the scope where no technical contradiction occurs, the matters described for a specific embodiment can be applied to other embodiments. In addition, each component may have the same characteristics as other components having the same name but different reference symbols. It is clear from the description of the claims that the forms after adding such modifications or improvements can also be included in the technical scope of the present invention.

[0140] Regarding the execution order of each process such as actions, operations, steps, and stages in the apparatus, system, program, and method shown in the claims, specification, and drawings, it should be noted that as long as it is not specifically stated as "earlier than ~", "before ~", etc., and the output of the previous process is not used in the subsequent process, it can be implemented in any order. Regarding the action flow in the claims, specification, and drawings, for the convenience of explanation, expressions such as "First," "Next," etc. are used for description, but it is not intended to mean that it must be implemented in that order. [Description of Symbols]

[0141] 10: Object to be cleaned 100: Semiconductor mounting substrate 110: Semiconductor substrate 112: Electrode 120: Temporary bonding material 130: Support 140: Semiconductor substrate before thinning 150: Temporary bonding material

Claims

1. A cleaning agent composition for semiconductor cleaning, which contains a quaternary ammonium salt, and an acid amide compound represented by the following Chemical Formula 1, [Chemical Formula 1] [Chemical Formula 1] Here, R1 to R3 are organic groups, and R1 contains at least one heteroatom, and Chemical Formula 1 does not contain a cyclic structure in which two or more groups selected from R1 to R3 are connected.

2. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein R1 has 4 or more carbon atoms.

3. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein R1 contains an -R-O-R' structure, and R and R' are alkyl groups.

4. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein at least one of R2 and R3 has 5 or more carbon atoms.

5. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein R2 and R3 are alkyl groups.

6. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein The quaternary ammonium salt is a first ammonium salt, and the first ammonium salt is represented by R A R B R C R D N + F - and R A ~R D are each independently selected from alkyl, aryl and aralkyl.

7. The cleaning agent composition for semiconductor cleaning according to claim 6, which contains 0.1 to 20.0% by mass of the first ammonium salt based on the total cleaning agent composition.

8. The cleaning agent composition for semiconductor cleaning according to claim 1, wherein the quaternary ammonium salt contains a first ammonium salt and a second ammonium salt, The first ammonium salt is represented by R A R B R C R D N + F - and R A ~R D are each independently selected from alkyl, aryl and aralkyl; The second ammonium salt is represented by R E R F R G R H N + X - and R E ~R H are each independently selected from alkyl, aryl and aralkyl, and X is selected from Cl, Br, I and OH.

9. The cleaning agent composition for semiconductor cleaning according to claim 8, which contains 0.1 to 20.0% by mass of the first ammonium salt based on the total cleaning agent composition.

10. The cleaning agent composition for semiconductor cleaning according to claim 8, which contains 0.1 to 5.0% by mass of the second ammonium salt based on the total cleaning agent composition.

11. The cleaning agent composition for semiconductor cleaning according to claim 1, which further contains a non-polar solvent.

12. The cleaning agent composition for semiconductor cleaning according to claim 11, wherein the non-polar solvent does not contain a heteroatom.

13. The cleaning agent composition for semiconductor cleaning according to claim 11, which contains 75.0 to 99.8% by mass of the acid amide compound and the non-polar solvent in total based on the total cleaning agent composition.

14. The cleaning agent composition for semiconductor cleaning according to claim 8, which further contains an ether component.

15. The cleaning agent composition for semiconductor cleaning according to claim 14, which contains 0.1 to 5.0% by mass of the ether component based on the total cleaning agent composition.

16. The cleaning agent composition for semiconductor cleaning according to claim 1, which has a water content of less than 4.0% by mass.

17. The cleaning agent composition for semiconductor cleaning according to claim 1, which is used for cleaning a silicone-containing temporary adhesive material remaining on a semiconductor substrate.

18. A method for cleaning a semiconductor substrate, which cleans the semiconductor substrate by applying the cleaning agent composition according to any one of claims 1 to 17 to a semiconductor substrate having a silicone-containing temporary adhesive material remaining on at least one surface.

19. A method for manufacturing a semiconductor mounting substrate, which includes the following stages: Bonding stage: Using a silicone-containing temporary adhesive material, bond the circuit surface of the semiconductor substrate before thinning, on which a circuit is formed on one surface, to the support body; Thinning stage: Thin the opposite surface of the circuit surface of the semiconductor substrate before thinning to form a semiconductor substrate; Electrode formation stage: Form an electrode on the opposite surface of the semiconductor substrate; Peeling stage: Peel the semiconductor substrate from the support body; And Cleaning stage: Use the cleaning agent composition according to any one of claims 1 to 17 to clean the semiconductor substrate after peeling.

Images