Cleaning agent composition for semiconductor cleaning and cleaning method of semiconductor substrate

Abstract

To provide a cleaning agent composition used for removing a temporary adhesive material containing a silicone compound present on a semiconductor substrate, and a cleaning method of a semiconductor substrate.SOLUTION: A cleaning agent composition for semiconductor cleaning, includes: a quaternary ammonium salt; and an acid amide compound represented by the following chemical formula. Here, R1 to R3 are organic groups, the R1 includes at least one heteroatom, and Chemical Formula 1 does not include a cyclic structure in which two or more selected from R1 to R3 are linked.SELECTED DRAWING: None

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] Patent Document 1 discloses a cleaning agent composition used for removing a temporary adhesive containing a silicone compound present on a substrate, wherein the cleaning agent composition (A) an organic solvent: 75 to 99 parts by mass, (B) water: 0 to 5 parts by mass, (C) an ammonium salt: 1 to 20 parts by mass and contains (where (A)+(B)+(C)=100 parts by mass). The organic solvent does not contain an organic solvent having a hydroxyl group, and contains 50 parts by mass or more of an organic solvent having a heteroatom in 100 parts by mass of the organic solvent. The cleaning agent composition is characterized in that the ammonium salt contains at least one of hydroxide ions, fluoride ions and chloride ions. (Claim 1) Patent Document 2 discloses a composition containing a quaternary alkylammonium fluoride or a hydrate of a quaternary alkylammonium fluoride and an aprotic solvent, wherein the aprotic solvent (A) an N-substituted amide compound having 4 or more carbon atoms having no active hydrogen on a nitrogen atom, and (B) an ether compound is included. (Claim 1) Patent Document 3 discloses a cleaning agent composition used for removing an adhesive residue, which contains a quaternary ammonium salt and a solvent containing a first organic solvent and a second organic solvent, wherein the first organic solvent is an acid amide derivative represented by the formula (Z), and the second organic solvent is another organic solvent different from the acid amide derivative. A detergent composition characterized by having a water content of less than 4.0% by mass. (Claim 1) is disclosed. [Prior art documents] [Patent documents] [Patent Document 1] WO2020 / 235605 [Patent Document 2] WO2020 / 080060 [Patent Document 3] WO2021 / 100651 [Summary of the Invention] [Means for Solving the Problems]

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

[0004] In the above, R1 may have 4 or more carbon atoms.

[0005] In the above, R1 includes an -R-O-R' structure, and R and R' may be alkyl groups.

[0006] In the above, at least one of R2 and R3 may have 5 or more carbon atoms.

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

[0008] In the above, the quaternary ammonium salt is R A R B R C R D N + F - It may be represented by. Here, R A ~R Dmay each independently be selected from an alkyl group, an aryl group, and an aralkyl group.

[0009] In the above, the quaternary ammonium salt may include 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 may each independently be selected from an alkyl group, an aryl group, and an aralkyl group. The second ammonium salt is represented by R E R F R G R H N + X - and R E ~R H may each independently be selected from an alkyl group, an aryl group, and an aralkyl group, and X may be selected from Cl, Br, I, and OH.

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

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

[0012] In the above, the detergent composition may further contain a nonpolar solvent.

[0013] In the above, the nonpolar solvent may not contain a heteroatom.

[0014] In the above, the detergent composition may contain the acid amide compound and the nonpolar solvent in a total amount of 75.0 to 99.8% by mass based on the total amount of the detergent composition.

[0015] In the above, the detergent composition may further contain an ether component.

[0016] In the above, the detergent composition may contain an ether component in an amount of 0.1 to 5.0% by mass based on the entire detergent composition.

[0017] In the above, the detergent composition may have a water content of less than 4.0% by mass.

[0018] In the above, the detergent composition may be used for cleaning a silicone-containing temporary adhesive material remaining on a semiconductor substrate.

[0019] In a second aspect of the present invention, a method for cleaning a semiconductor substrate is provided. The cleaning method may include cleaning the semiconductor substrate having a silicone-containing temporary adhesive material remaining on at least one side thereof by applying a detergent composition. The detergent composition may be the one described above.

[0020] Note that the above summary of the invention does not list all the necessary features of the present invention. Also, sub-combinations of these feature groups may also be inventions.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Figure 3

Figure 4

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Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0022] Hereinafter, the present invention will be described through embodiments of the invention. However, the following embodiments do not limit the invention according to the claims. Not all combinations of features described in the embodiments are essential for the solution means of the invention. Also, referring to the drawings, the embodiments will be described. In the description of the drawings, the same or similar parts may be given the same reference numerals and redundant descriptions may be omitted.

[0023] [Overview of the object to be cleaned 10] FIG. 1 schematically shows an example of the object to be cleaned 10 of the cleaning composition in the present embodiment. The object to be cleaned 10 is an object to be cleaned by the cleaning composition. The object to be cleaned 10 may be various objects with 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 by the cleaning composition.

[0024] For example, the object to be cleaned 10 may be a semiconductor substrate with a silicone-containing temporary adhesive material remaining on at least one side. For example, the semiconductor substrate may be reinforced by a support during electrode formation or the like, and a silicone-containing temporary adhesive material used for bonding to the support may remain. In the example of FIG. 1, 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 with a circuit (not shown) formed on one side (for example, the upper side in FIG. 1). 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 provided on the surface of the semiconductor substrate 110 such as a surface bump.

[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 remain on the circuit surface side of the semiconductor substrate 110. It is provided for bonding to a support in the manufacturing process of the semiconductor mounting substrate described later, and the temporary adhesive material 120 remains after the support is peeled off. When the temporary adhesive material 120 is cleaned and removed by the cleaning agent composition of the present embodiment, the semiconductor mounting substrate is completed.

[0028] [Overview of the cleaning agent composition] The cleaning agent composition in the present embodiment will be described. The cleaning agent composition may be mainly used for semiconductor cleaning. In particular, the cleaning agent composition may 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 (3) a non-polar solvent and / or (4) one or both of an ether component.

[0029] [Regarding (1) Quaternary ammonium salt] The quaternary ammonium salt may contain only the first ammonium salt (one type). Instead of this, the quaternary ammonium salt may contain the first ammonium salt and the second ammonium salt (two types).

[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 may be monocyclic or polycyclic with carbon atoms from 5 to 30 (preferably 6 to 12). For example, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group. The aryl group may be unsubstituted or substituted by an alkyl group or other functional groups.

[0033] The aralkyl group may be one in which the hydrogen of the alkyl group described above is substituted by the above aryl group.

[0034] As an example, the first ammonium salt is a compound in which R A ~R D is a methyl group, a compound in which R A ~R D is an ethyl group, a compound in which R A ~R D is a propyl group, a compound in which R A ~R D is an isopropyl group, a compound in which R A ~R D is an n-butyl group, a compound in which RA ~R D is a compound in which ~R is an isobutyl group, R A ~R D is a compound in which ~R is a sec-butyl group, or R A ~R D may be a compound in which ~R is a tert-butyl group.

[0035] The first ammonium salt may be a hydrate. Alternatively, the first ammonium salt may be an anhydride.

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

[0037] By including the first ammonium salt contained in the detergent composition, the detergency of the detergent composition can be enhanced. In particular, the first ammonium salt containing fluoride ions contributes to dissolving / decomposing the silicone-containing temporary adhesive material.

[0038] The second ammonium salt is R E R F R G R H N + X - represented by. 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 may be the same as those described for the first ammonium salt. X may be selected from Cl, Br, I, and OH. Preferably, X is Cl, Br, or I.

[0039] The second ammonium salt may be a hydrate. Alternatively, the second ammonium salt may be an anhydride.

[0040] The detergent composition may contain the second ammonium salt in an amount of 0.1 to 5.0% by mass, preferably 1 to 4% by mass, based on the total amount of the detergent composition.

[0041] The second ammonium salt can reduce the polarity of the detergent composition while enhancing the cleaning ability of the first ammonium salt. By including the second ammonium salt in the detergent composition, the polarity of the detergent composition can be suppressed compared to the case of only the first ammonium salt, making it easier for the detergent composition to penetrate the temporary adhesive material containing silicone and making it easier for the decomposition products to dissolve in the detergent composition.

[0042] The quaternary ammonium salt may further contain another ammonium salt in addition to the first ammonium salt and the second ammonium salt.

[0043] [(2) Regarding 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 Structure Diagram]

[0044] In Chemical Formula 1, R1 to R3 are organic groups. Chemical Formula 1 does not include a cyclic structure in which two or more of R1 to R3 are linked. For example, Chemical Formula 1 does not include 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] The acid amide compound increases the polarity of the detergent composition. When the detergent composition does not contain the acid amide compound, the polarity deviates too much between the quaternary ammonium salt (especially the first ammonium salt) and other components, which may cause phase separation or hinder the penetration into the temporary adhesive material. If R1 to R3 form a cyclic structure, the permeability to the temporary adhesive material may decrease, but according to this embodiment, by excluding such a cyclic structure, the permeability to the temporary adhesive material can be increased. Furthermore, by including the acid amide compound, the decomposition products can be made more easily soluble in the detergent composition.

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

[0047] For example, R and R' may each independently be selected from 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' may have the same structure. Or R and R' may have different structures. Strictly speaking, R is a divalent alkylene group, but R may have a structure obtained by removing hydrogen from the alkyl groups listed above.

[0049] R2 and R3 are alkyl groups. R2 and R3 may be linear, branched, and / or cyclic alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms). For example, at least one of R2 and R3 may have 1 or more, 3 or more, or 5 or more carbon atoms.

[0050] R2 and R3 may be selected from 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 compounds are 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-propoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-pentoxy-N,N-dimethylpropanamide, 3-hexoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-diethylpropanamide, 3-ethoxy-N,N-diethylpropanamide, 3-propoxy-N,N-diethylpropanamide, 3-butoxy-N,N-diethylpropanamide, 3-pentoxy-N,N-diethylpropanamide, 3-hexoxy-N,N-diethylpropanamide, 3-methoxy-N,N-dipropylpropanamide, 3-ethoxy-N,N-dipropylpropanamide, 3-propoxy-N,N-dipropylpropanamide, 3-butoxy-N,N-dipropylpropanamide, 3-pentoxy-N,N-dipropylpropanamide, 3-hexoxy-N,N-dipropylpropanamide, 3-methoxy-N,N-dibutylpropanamide, 3-ethoxy-N,N-dibutylpropanamide, 3-propoxy-N,N-dibutylpropanamide, 3-butoxy-N,N-dibutylpropanamide, 3-pentoxy-N,N-dibutylpropanamide, 3-hexoxy-N,N-dibutylpropanamide, 3-methoxy-N,N-dipentylpropanamide, 3-ethoxy-N,N-dipentylpropanamide, 3-propoxy-N,N-dipentylpropanamide, 3-butoxy-N,N-dipentylpropanamide, 3-pentoxy-N,N-dipentylpropanamide, 3-hexoxy-N,N-dipentylpropanamide, 4-methoxy-N,N-dimethylbutanamide, 4-ethoxy-N,N-dimethylbutanamide, 4-propoxy-N,N-dimethylbutanamide, 4-butoxy-N,N-dimethylbutanamide, 4-pentoxy-N,N-dimethylbutanamide, 4-hexoxy-N,N-dimethylbutanamide, 4-methoxy-N,N-diethylbutanamide, 4-ethoxy-N,N-diethylbutanamide, 4-propoxy-N,N-diethylbutanamide, 4-butoxy-N,N-diethylbutanamide, 4-pentoxy-N,N-diethylbutanamide, 4-hexoxy-N,N-diethylbutanamide, 4-methoxy-N,N-dipropylbutanamide, 4-ethoxy-N,N-dipropylbutanamide, 4-propoxy-N,N-dipropylbutanamide, 4-butoxy-N,N-dipropylbutanamide, 4-pentoxy-N,N-dipropylbutanamide, 4-hexoxy-N,N-dipropylbutanamide, 4-methoxy-N,N-dibutylbutanamide, 4-ethoxy-N,N-dibutylbutanamide, 4-propoxy-N,N-dibutylbutanamide, 4-butoxy-N,N-dibutylbutanamide, 4-pentoxy-N,N-dibutylbutanamide, 4-hexoxy-N,N-dibutylbutanamide, 4-methoxy-N,N-dipentylbutanamide, 4-ethoxy-N,N-dipentylbutanamide, 4-propoxy-N,N-dipentylbutanamide, 4-butoxy-N,N-dipentylbutanamide, 4-pentoxy-N,N-dipentylbutanamide, or 4-hexoxy-N,N-dipentylbutanamide may be used.,

[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 entire cleaning composition.,

[0053] [(3) Regarding nonpolar solvents] The nonpolar solvent is an organic solvent having no polarity or very low polarity. The nonpolar solvent may be selected from those generally known as nonpolar solvents. The nonpolar solvent may not contain heteroatoms. The nonpolar solvent may be an unsubstituted alkane, alkene, or aryl. As an example, the nonpolar 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 decahydronaphthalene, 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, diphenylmethane, 1,4-terpin, 1,8-terpin, bornane, norbornane, pinane, tsujan, carane, longifolene, geraniol, nerol, 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, tsyone, 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 tetrahydronaphthalene, etc.

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

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

[0062] The alkyl ether may be an ether composed of 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 an aryl ether compound such as anisole or 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, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, or diphenyl ether.

[0065] The ether can adjust the polarity of the detergent composition. By including the ether in the detergent composition, a certain degree of polarity is imparted to the detergent composition, preventing phase separation of the quaternary ammonium salt (especially the primary ammonium salt) and the nonpolar solvent in the detergent composition, and assisting the penetration of the quaternary ammonium salt (especially the primary ammonium salt) into the pressure-sensitive adhesive material.

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

[0067] The method for preparing the cleaning composition is not particularly limited. The cleaning composition may be produced by mixing the above components. The mixing order is not particularly limited. The cleaning composition may have a flash point of 21°C or higher. When the flash point is within the above range, the cleaning of the object to be cleaned 10 can be performed safely.

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

[0069] FIG. 2 shows the flow of the method for manufacturing a semiconductor mounting substrate using the cleaning composition of the present embodiment. For example, by executing each process of S100 to S500, a semiconductor mounting substrate is manufactured. A part of S100 to S500 may be omitted. Other processes may be executed as needed in addition to S100 to S500.

[0070] First, in S100, a bonding step is executed in which the circuit surface of a semiconductor substrate having a circuit formed on one side and a support are bonded with a silicone-containing temporary bonding material. FIG. 3 shows a semiconductor substrate 140 before thinning bonded with a support 130 and a silicone-containing temporary bonding material 150.

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

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

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

[0074] Here, 1 R 2 R 3 R 4 R 5 and 6 R 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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, and groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms. Among these, methyl group and phenyl group are preferable.

[0075] The uncured composition may include, for example, (A-1) an organopolysiloxane having two or more alkenyl groups in one molecule, (A-2) an organohydrogenpolysiloxane containing hydrogen atoms (Si-H groups) bonded to two or more silicon atoms 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. The uncured composition may also contain (A-4) an organic solvent or (A-5) a reaction controller.

[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) preferably contains 0.6 mol% or more and 9 mol% or less (mole number of alkenyl groups / mole number of Si) of alkenyl groups in one molecule.

[0077] Such organopolysiloxanes are specifically represented by the following formulas (1), (2), and (3). These may be used alone or in combination of two or more. R 7 (3-a) Z a SiO-(R 7 ZSiO) m -(R 7 2SiO) 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 3SiO1 / 2 ) c (R 7 (3-e) Z e SiO 1 / 2 ) d (3)

[0078] In the above formula, R 7 each independently represents a monovalent hydrocarbon group having no aliphatic unsaturated bond, Z each independently represents an alkenyl group-containing monovalent organic group, a is an integer of 0 to 3, m and n are such that 2a + m is a number such that the alkenyl group content in one molecule is 0.6 mol% or more and 9 mol% or less. p and q are such that p + 2 is a number such that the alkenyl group content in one molecule is 0.6 mol% or more and 9 mol% or less. e is 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 above formula, R 7 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specifically, R 7 includes alkyl groups such as methyl group, ethyl group, propyl group, butyl group; cycloalkyl groups such as cyclohexyl group; aryl groups such as phenyl group, tolyl group, etc. Among these, an alkyl group or a phenyl group is preferred.

[0080] Z is preferably an organic group having 2 to 10 carbon atoms. Z includes alkenyl groups such as vinyl group, allyl group, hexenyl group, octenyl group; (meth)acryloylalkyl groups such as acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group; (meth)acryloxyalkyl groups such as acryloxypropyl group, acryloxyethyl group, methacryloxypropyl group, methacryloxyethyl group; cyclohexenylethyl group, vinyloxypropyl group, etc. Among these, a vinyl group is preferred industrially.

[0081] In the above formula (1), if a is 1 to 3, the molecular chain end is blocked by an alkenyl group. This reactive molecular chain end alkenyl group is preferable because the reaction can be completed in a short time. Further, industrially and in terms of cost, a = 1 is preferable. The property of this alkenyl group-containing diorganopolysiloxane is preferably oily or raw rubber-like.

[0082] The above formula (3) represents an organopolysiloxane having a resin structure. In the above formula (3), industrially and in terms of cost, e = 1 is preferable. Further, 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. This organopolysiloxane having a resin structure may be used as a solution dissolved in an organic solvent.

[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. This organohydrogenpolysiloxane is linear, branched or cyclic. For example, those having at least 2, more preferably 2 or more and 100 or less, still more preferably 3 or more and 50 or less hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and linear, branched or cyclic ones 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. This organohydrogenpolysiloxane may be used alone or in combination of two or more.

[0085] Component (A-2) is desirably blended in an amount such that the molar ratio of the Si-H groups in component (A-2) to the alkenyl groups in component (A-1) (Si-H groups / alkenyl groups) is preferably 0.3 or more and 10 or less, more preferably 1.0 or more and 8.0 or less. If this molar ratio is 0.3 or more, the crosslinking density does not become too low, and the uncured composition layer can also be suitably cured. If the molar ratio is 10 or less, the crosslinking density does not become too high, and sufficient adhesiveness and tack can be obtained. Also, if the molar ratio is 10 or less, the pot life of the uncured composition can be extended.

[0086] Component (A-3) is a platinum-based catalyst (i.e., a platinum group metal catalyst). Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and a reaction product of chloroplatinic acid and a vinyl group-containing siloxane. The platinum-based catalyst may be used alone or in combination of two or more. Component (A-3) is desirably blended in an amount such that, in terms of the platinum group metal content (in terms of mass), it is preferably 1 ppm or more and 5,000 ppm or less, more preferably 5 ppm or more and 2,000 ppm or less, based on the total of component (A-1) and component (A-2). If it is 1 ppm or more, the curability of the uncured composition layer is less likely to decrease. Therefore, it is possible to suppress both a decrease in crosslinking density and a decrease in holding power. If it is 5,000 ppm or less, the pot life of the uncured composition can be extended.

[0087] Component (A-4) is an organic solvent. The organic solvent is not particularly limited 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 may be used alone or in combination of two or more.

[0088] When using component (A-4), component (A-4) is preferably blended in an amount of 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, still more preferably 40 parts by mass or more and 300 parts by mass or less, based on 100 parts by mass in total of components (A-1) and (A-2).

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

[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-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxysiloxycyclohexane, bis(2,2-dimethyl-3-butynoxy)dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, and the like. Among these, 1-ethynylcyclohexanol and 3-methyl-1-butyn-3-ol are preferred. The reaction control agent may be used alone or in combination of two or more.

[0091] When using component (A-5), component (A-5) is preferably blended in an amount of 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.05 parts by mass or more and 2.0 parts by mass or less, based on 100 parts by mass in total of components (A-1) and (A-2). If it is 8.0 parts by mass or less, the curability of the uncured composition layer is less likely to decrease. If it is 0.01 parts by mass or more, the effect of reaction control is sufficiently exerted.

[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 esters, halogen-based, phosphorus-based, and antimony-based flame retardants; antistatic agents such as cationic surfactants, anionic surfactants, and nonionic surfactants. These other components may be used individually or in combination of two or more. The other components are incorporated within a range that does not inhibit the object of the present invention. For example, when using a filler to enhance heat resistance, it is preferable to incorporate the filler in an amount of 50 parts by mass or less based on 100 parts by mass in total of component (A-1) and component (A-2).

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

[0094] The bonding may be performed by applying the uncured composition on the support 130, drying it, laminating the pre-thinning semiconductor substrate 140 on the uncured composition, and then thermally curing it. The application of the uncured composition may be carried out by spin coating, slit coating, or spray coating. The drying may 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, according to the volatilization conditions of the solvent contained in the uncured composition. Instead of applying and drying the uncured composition, a film of the pre-cured or semi-cured uncured composition may be sandwiched between the support 130 and the pre-thinning semiconductor substrate 140.

[0095] The bonding may be performed under reduced pressure and / or increased pressure, and may further be performed under heating (for example, 40 to 250 °C) as necessary. The bonding may be performed using a commercially available wafer bonding apparatus (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 may be performed under conditions where the uncured composition is sufficiently cured. For example, the thermosetting may be performed at 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 step of thinning the opposite surface of the circuit surface (the surface on the support 130 side) of the semiconductor substrate 140 before thinning is executed. After the thinning step, the semiconductor substrate 140 before thinning becomes the semiconductor substrate 110 thinned as shown in FIG. 4.

[0098] The thinning may be performed by cutting and / or polishing. The thinning may be performed such that the thickness of the semiconductor substrate 110 is, for example, 5 μm or more and 300 μm or less, preferably 10 μm or more and 100 μm or less. There is no particular limitation on the method of cutting and / or polishing, and it can be performed by a known method. For example, polishing may be performed while spraying water on the substrate and the grindstone (such as diamond) for cooling. For example, the back surface of the substrate may be polished by CMP. Further, for example, cutting may be performed using a known grinding apparatus (as an example, DAG-810 (trade name) manufactured by DISCO Corporation).

[0099] Next, in S300, an electrode forming step of forming an electrode on the opposite surface of the circuit surface of the semiconductor substrate 110 is executed. An electrode 112 penetrating the semiconductor substrate 110 is formed as shown in FIG. 5.

[0100] For example, a through electrode (TSV) may be provided as the electrode 112. A surface electrode may 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 may be performed on the surface of the semiconductor substrate 110 (the surface opposite to the temporary adhesive material 150). For example, in addition to electrode formation, metal circuit formation, protective film formation, and / or dicing may be performed. In these processes, necessary processes such as metal sputtering, wet / dry etching, photolithography, and / or surface oxidation treatment of semiconductors such as silicon may be executed.

[0102] Next, in S400, a peeling step of peeling the semiconductor substrate 110 from the support 130 is executed. By executing the peeling step, the support 130 is separated from the semiconductor substrate 110.

[0103] The peeling step may be executed in a low-temperature environment of about room temperature to 60°C. The peeling step may be executed by a lifting method, a peeling method, or a solvent peeling method. The lifting method may be performed by fixing one of the semiconductor substrate 110 or the support 130 horizontally and lifting the other at a certain angle from the horizontal direction.

[0104] The peeling method may be executed by adhering a dicing tape to the surface of the semiconductor substrate 110 (the surface opposite to the temporary adhesive material 150), vacuum-adsorbing the dicing tape surface to the adsorption surface, and peeling the support 130 from the semiconductor substrate 110 by peeling off.

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

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

[0107] Next, in S500, a cleaning step of cleaning the semiconductor substrate 110 after peeling using the above cleaning composition is performed. That is, the semiconductor substrate 110 with the silicone-containing temporary adhesive material remaining on at least one side is cleaned by applying the cleaning composition. The cleaning method performed in the following cleaning step will be described in more detail.

[0108] [Outline of the cleaning method of the semiconductor substrate] FIG. 6 shows an example of a sub-flow of the cleaning step (S500). The cleaning method (S500) of the semiconductor substrate 110 may be performed by executing a part or all of S510 to S550.

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

[0110] In S530, rinsing of the semiconductor substrate 110 after cleaning is performed. For example, the semiconductor substrate 110 is cleaned with a rinsing solution to remove the cleaning composition. The rinsing solution may be water or alcohol, for example, isopropanol.

[0111] In S550, the semiconductor substrate 110 after rinsing is dried. The drying may be performed under conditions where the rinsing solution is sufficiently dried, for example, at 30 to 100 ° C for 1 to 10 minutes.

[0112] By executing each step from S100 to S500 in this manner, a semiconductor mounting substrate 100 can be manufactured in which the temporary adhesive material 120 is sufficiently removed from the surface of the semiconductor substrate 110 as shown in FIG. 7. In particular, according to the present embodiment, by keeping the polarity of the cleaning agent composition within an appropriate range, the penetration power into the silicone-containing temporary adhesive material is increased, and the silicone-containing temporary adhesive material can be strongly cleaned and removed by taking advantage of the cleaning power of the quaternary ammonium salt (especially the primary ammonium salt). As a result, a semiconductor mounting substrate 100 in which there is no residue of the temporary adhesive material 120 or the residue of the adhesive material is extremely small can be obtained.

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

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

[0115] The mixing was carried out by the following method. First, the quaternary ammonium salt of (1-1) was added to the (2) acid amide compound and stirred and dissolved sufficiently. Next, the quaternary ammonium salt of (1-2) was added and stirred and dissolved sufficiently.

[0116] (Preparation Example 2) The following raw materials were mixed to obtain a cleaning agent composition 2. The mixing was carried out in the same procedure as for the cleaning composition 1. (1-1) Tetrabutylammonium fluoride (TBAF) trihydrate 4.5% by mass (1-2) Quaternary ammonium salt represented by chemical formula A 0.5% by mass (2) 95% by mass of 3-methoxy-N,N-dimethylpropanamide

[0117] (Preparation Example 3) The following raw materials were mixed to obtain Detergent Composition 3. The mixing was carried out in 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) The following raw materials were mixed to obtain Detergent Composition 4. After the mixing was carried out in the same procedure as Detergent Composition 1, the non-polar solvent in (3) was added and stirred well until dissolved. (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) The following raw materials were mixed to obtain Detergent Composition 5. The mixing was carried out in the same procedure as Detergent Composition 4. (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 ethylcyclohexane

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

[0121] The mixing was carried out as follows. First, the quaternary ammonium salt of (1-1) was added to the (2) acid amide compound, and it was sufficiently stirred and dissolved. Next, the ether component of (4) was added and it was sufficiently stirred and dissolved.

[0122] (Preparation Example 7) The following raw materials were mixed to obtain a detergent composition 7. (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 (9) 95% by mass of N,N-dimethyloctanamide

[0123] The mixing was carried out as follows. First, the quaternary ammonium salt of (1-1) was added to the (9) N,N-dimethyloctanamide, and it was sufficiently stirred and dissolved. Next, the quaternary ammonium salt of (1-2) was added and it was sufficiently stirred and dissolved.

[0124] [Example 1] An uncured composition was prepared as follows. To a solution consisting of 100 parts by mass of polydimethylsiloxane having 2.0 mol% of vinyl groups at both ends and side chains, and having a molecular end blocked with a SiMe2Vi group and a number average molecular weight (Mn) of 50,000 by GPC, and 400 parts by mass of isododecane, 3.5 parts (2 mol with respect to the alkenyl group) of an organohydrogenpolysiloxane represented by the following formula (M-1) and 0.7 part of ethynylcyclohexanol were added and mixed. Further, 0.5 part of a platinum catalyst CAT-PL-5 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and filtered through a 0.2 μm membrane filter to obtain an uncured composition.

[0125] A 200 mm glass wafer (thickness: 700 μm) was prepared as a support. After spin-coating the uncured composition on the support, it was heated on a hot plate at 100 °C for 5 minutes to form a layer of the temporary adhesive material (thickness: 35 μm). Subsequently, a 200 mm diameter silicon wafer (thickness: 725 μm) was used as a semiconductor substrate and bonded to the support. The bonding was performed using a wafer bonding apparatus (manufactured by EVG, EVG520IS (trade name)). The bonding temperature was 50 °C, the chamber internal pressure during bonding was 10−3 mbar or less, and the load was 10 kN. After bonding, the bonded semiconductor substrate was heated in an oven at 200 °C for 2 hours to cure the temporary adhesive material and then cooled to room temperature.

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

[0127] Subsequently, as a process corresponding to processing on the back surface of the semiconductor substrate, a simulated heating process was performed. Specifically, the semiconductor substrate subjected to back surface grinding was heated on a hot plate at 260 °C for 10 minutes.

[0128] The support was peeled off from the semiconductor substrate. Specifically, a dicing tape was attached to the back surface (non-circuit forming surface) of the silicon wafer using a dicing frame, and this dicing tape surface was set on a suction plate by vacuum suction. Thereafter, at room temperature, the glass wafer was lifted at one point with tweezers to peel off the glass wafer and the temporary adhesive material.

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

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

[0131] [Example 3] The same steps as in Example 1 were performed using Detergent Composition 3 instead of Detergent Composition 1.

[0132] [Example 4] The same steps as in Example 1 were performed using Detergent Composition 4 instead of Detergent Composition 1.

[0133] [Example 5] The same steps as in Example 1 were performed using Detergent Composition 5 instead of Detergent Composition 1.

[0134] [Example 6] The same steps as in Example 1 were performed using Detergent Composition 6 instead of Detergent Composition 1.

[0135] [Comparative Example] The same steps as in Example 1 were performed using Detergent Composition 7 instead of Detergent Composition 1.

[0136] [Analysis and Evaluation] Analysis and evaluation of the cleaning in the examples were carried out. The semiconductor substrates after cleaning in each example were analyzed by X-ray photoelectron spectroscopy (XPS) to analyze the elemental distribution on the surface. The measuring apparatus used was PHI Quantera SXM manufactured by ULVAC-PHI, Inc. Monochromatic Alkα was used as the X-ray source, and the analysis was performed with an output of 25 W (15 kV, 100 μm diameter), a photoelectron extraction angle of 45°, a pass energy of 55.0 eV, and a step resolution of 0.05 eV.

[0137] The Si content in each example is shown in the following table. The Si content in the table excludes Si derived from the silicon substrate.

Table 1

[0138] As shown in Table 1, in Examples 1 to 6 that satisfy the requirements of the present invention, good detergency was obtained in a short time with respect to the temporary adhesive containing silicone remaining on the substrate. Therefore, the subsequent semiconductor processing process can be carried out well. On the other hand, in the comparative example where the acid amide compound has no heteroatom, a large amount of Si remained, indicating poor detergency. The substrate washed in the comparative example could not be used in the subsequent semiconductor processing process.

[0139] As described above, the present invention has been described using embodiments, but the technical scope of the present invention is not limited to the scope described in the above embodiments. It is obvious to those skilled in the art that various changes or improvements can be made to the above embodiments. Also, within a technically consistent range, matters described for a specific embodiment can be applied to other embodiments. Further, each component may have the same features as other components with the same name but different reference numerals. It is clear from the description of the claims that such modified or improved forms can also be included in the technical scope of the present invention.

[0140] It should be noted that the execution order of each process such as operations, procedures, steps, and stages in the devices, systems, programs, and methods shown in the claims, the specification, and the drawings is not explicitly indicated as "earlier" or "preceding" etc., and can be realized in any order unless the output of the previous process is used in the subsequent process. Regarding the operation flows in the claims, the specification, and the drawings, even if "first," "next," etc. are used for convenience of explanation, it does not mean that it is essential to carry out in this order.

Explanation of Reference Numerals

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

Claims

1. A quaternary ammonium salt, an acid amide compound represented by the following chemical formula 1, and a cleaning agent composition for semiconductor cleaning containing the same: [Chemical formula 1] 【Chemical 1】 Here, R １ ~R ３ is an organic group, and R １ contains at least one heteroatom, Chemical formula 1 is R １ ~R ３ does not include a cyclic structure in which two or more selected from them are linked.

2. R １ has 4 or more carbon atoms, The cleaning agent composition for semiconductor cleaning according to Claim 1.

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

4. R ２ and R ３ at least one of which has 5 or more carbon atoms, The cleaning agent composition for semiconductor cleaning according to Claim 1.

5. R ２ and R ３ is an alkyl group, The cleaning agent composition for semiconductor cleaning according to Claim 1.

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

7. The cleaning agent composition for semiconductor cleaning according to Claim 6, containing 0.1 to 20.0% by mass of the first ammonium salt in the whole cleaning agent composition.

8. The cleaning agent composition for semiconductor cleaning according to Claim 1, wherein the quaternary ammonium salt contains

9. R Ａ R Ｂ R Ｃ R Ｄ N ＋ F － is represented by, and R Ａ to R Ｄ are each independently a first ammonium salt selected from an alkyl group, an aryl group, and an aralkyl group, and R Ｅ R Ｆ R Ｇ R Ｈ N ＋ X － represented by, R Ｅ to R Ｈ are each independently selected from an alkyl group, an aryl group, and an aralkyl group, and X is a second ammonium salt selected from Cl, Br, I, and OH, and The cleaning agent composition for semiconductor cleaning according to Claim 8, containing 0.1 to 20.0% by mass of the first ammonium salt in the whole cleaning agent composition.

10. The cleaning agent composition for semiconductor cleaning according to Claim 8, containing 0.1 to 5.0% by mass of the second ammonium salt in the whole cleaning agent composition.

11. The cleaning agent composition for semiconductor cleaning according to Claim 1, further containing a non-polar solvent.

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

13. The cleaning agent composition for semiconductor cleaning according to Claim 11, containing a total of 75.0 to 99.8% by mass of the acid amide compound and the non-polar solvent in the whole cleaning agent composition.

14. The cleaning agent composition for semiconductor cleaning according to Claim 8, further containing an ether component.

15. The cleaning agent composition for semiconductor cleaning according to Claim 14, containing 0.1 to 5.0% by mass of the ether component in the whole cleaning agent composition.

16. The cleaning agent composition for semiconductor cleaning according to Claim 1, having 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, comprising 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 side thereof to clean the semiconductor substrate.

19. A bonding step of bonding a circuit surface of a pre-thinning semiconductor substrate having a circuit formed on one side and a support with a silicone-containing temporary adhesive material ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ A thinning step of thinning the opposite surface of the circuit surface of the semiconductor substrate before thinning to form a semiconductor substrate; An electrode forming step of forming an electrode on the opposite surface of the semiconductor substrate; A peeling step of peeling the semiconductor substrate from the support; A cleaning step of cleaning the semiconductor substrate after peeling using the cleaning agent composition according to any one of claims 1 to 17; A method for manufacturing a semiconductor mounting substrate including the above steps.

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