JP7498427B2 - Cleaning composition and method for producing processed semiconductor substrate - Google Patents

Description

The present invention relates to a cleaning composition used to remove adhesive residues after peeling off a temporary adhesive layer formed on a semiconductor substrate using a polysiloxane adhesive.

Conventionally, semiconductor wafers have been integrated in a two-dimensional plane, but there is a demand for semiconductor integration technology that integrates (stacking) the plane in a three-dimensional direction for even greater integration. This three-dimensional stacking is a technology that integrates multiple layers while connecting them with through silicon vias (TSVs). When integrating multiple layers, each wafer to be integrated is thinned by polishing the side opposite the circuit surface (i.e., the back side), and the thinned semiconductor wafers are stacked.

Semiconductor wafers before thinning (also simply called wafers here) are attached to a support in order to be polished with a polishing device. The adhesive used at this time is called temporary adhesive because it must be easily peeled off after polishing. This temporary adhesive must be easily removed from the support, and if a large force is applied to remove it, the thinned semiconductor wafer may be cut or deformed, so it is easily removed to prevent such things from happening. However, it is undesirable for the semiconductor wafer to come loose or shift due to the polishing stress when polishing the back surface of the semiconductor wafer. Therefore, the performance required for temporary adhesive is to withstand the stress during polishing and to be easily removed after polishing. For example, it is required to have high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the vertical direction during removal. In addition, the processing process can reach high temperatures of 150°C or more, so heat resistance is also required.

Under such circumstances, in the semiconductor field, polysiloxane adhesives that can have these properties are mainly used as temporary adhesives. In polysiloxane-based adhesion using polysiloxane adhesives, adhesive residues often remain on the substrate surface after peeling off the thinned substrate. In order to avoid problems in the subsequent process, cleaning compositions have been developed to remove the residues and clean the semiconductor substrate surface (e.g., Patent Documents 1 and 2), and there is always a demand for new cleaning compositions in the semiconductor field these days. Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and a quaternary ammonium hydroxide, and Patent Document 2 discloses a cured resin remover containing an alkyl ammonium fluoride, but the emergence of a more effective cleaning composition is desired.
Incidentally, the semiconductor wafer is electrically connected to the semiconductor chip via bump balls made of a conductive material such as metal, and the use of chips equipped with such bump balls contributes to miniaturization of semiconductor packaging.
In this regard, bump balls made of metals such as copper and tin have poor corrosion resistance and therefore have the problem of being damaged by a cleaning composition used to remove adhesive residues from a support or wafer (Patent Document 3). Therefore, one of the required properties of a cleaning composition is that it does not corrode the bump balls.

International Publication No. 2014/092022 U.S. Patent No. 6,818,608 Korean Patent Publication No. 2018-0066550

The present invention has been made in consideration of the above circumstances, and aims to provide a cleaning composition that exhibits good cleaning properties for adhesive residues after peeling off a temporary adhesive layer obtained using a polysiloxane adhesive when cleaning a substrate such as a semiconductor substrate, and that has reduced corrosiveness to metals such as bump balls.

As a result of intensive research conducted by the present inventors to solve the above problems, it was discovered that, when cleaning a substrate such as a semiconductor substrate to which adhesive residues are attached after peeling off a temporary bond formed by an adhesive layer obtained using a polysiloxane adhesive, particularly an adhesive layer that is a cured film obtained from a siloxane adhesive containing a polysiloxane component that cures by a hydrosilylation reaction, a cleaning composition containing a quaternary ammonium salt, a metal corrosion inhibitor, and an organic solvent is used, by using a thiazole compound containing a carboxy hydrocarbon group as the metal corrosion inhibitor, it is possible to suppress the decrease in cleaning speed caused by the addition of the metal corrosion inhibitor, and as a result, it is possible to realize excellent cleaning performance and to suppress corrosion of metals such as bump balls, and thus the present invention has been completed.

（式中、Ｄ^１は、単結合、酸素原子又は硫黄原子を表し、Ｄ^２は、カルボキシアルキル基又はカルボキシアルケニル基を表し、Ｄ^３は、ベンゼン環に置換する置換基を表し、互いに独立して、ハロゲン原子、ヒドロキシ基、アルキル基、アリール基、アルコキシ基又はアリールオキシを表し、ｄは、置換基の数を表し、０～４の整数である。）
８．上記カルボキシ炭化水素基を含むチアゾール系化合物が、３－（２－ベンゾチアゾリルチオ）プロピオン酸を含む１の洗浄剤組成物、
９．上記第四級アンモニウム塩が、含ハロゲン第四級アンモニウム塩である１～８のいずれかの洗浄剤組成物、
１０．上記含ハロゲン第四級アンモニウム塩が、含フッ素第四級アンモニウム塩である９の洗浄剤組成物、
１１．上記含フッ素第四級アンモニウム塩が、フッ化テトラ（炭化水素）アンモニウムである１０の洗浄剤組成物、
１２．上記フッ化テトラ（炭化水素）アンモニウムが、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化テトラプロピルアンモニウム及びフッ化テトラブチルアンモニウムからなる群から選ばれる少なくとも１種を含む１１の洗浄剤組成物、
１３．上記基体上に残留するポリシロキサン系接着剤が、ヒドロシリル化反応により硬化する成分（Ａ）を含む接着剤組成物から得られた接着層の接着剤残留物である１～１２のいずれかの洗浄剤組成物、
１４．バンプボールを有する半導体基板と、支持基板と、接着剤組成物から得られる接着層とを備える積層体を製造する第１工程、得られた積層体の半導体基板を加工する第２工程、加工後に半導体基板を剥離する第３工程、及び剥離した半導体基板上に残存する接着剤残留物を洗浄剤組成物により除去する第４工程を含む、加工された半導体基板の製造方法において、上記洗浄剤組成物として１～１３のいずれかの洗浄剤組成物を用いることを特徴とする、加工された半導体基板の製造方法
を提供する。 That is, the present invention provides
1. A cleaning composition used for removing adhesive residues, comprising a quaternary ammonium salt, a metal corrosion inhibitor comprising a thiazole compound containing a carboxy hydrocarbon group, and an organic solvent;
2. A cleaning composition in which the thiazole-based compound containing a carboxy hydrocarbon group contains at least one selected from the group consisting of a thiazole derivative containing a carboxy hydrocarbon group, an isothiazole derivative containing a carboxy hydrocarbon group, and a thiadiazole derivative containing a carboxy hydrocarbon group;
3. The cleaning composition according to 1 or 2, wherein the carboxy hydrocarbon group is a carboxy alkyl group or a carboxy alkenyl group.
4. The cleaning composition according to 3, wherein the carboxy hydrocarbon group is a carboxyalkyl group.
5. A cleaning composition according to claim 1, wherein the thiazole compound containing a carboxy hydrocarbon group has a structure in which a thiazole ring, an isothiazole ring or a thiadiazole ring is bonded to the carboxy hydrocarbon group directly or via an ether group or a thioether group.
6. The cleaning composition according to 5, wherein the thiazole compound containing a carboxy hydrocarbon group has a structure in which a thiazole ring and a carboxy hydrocarbon group are bonded directly or via an ether group or a thioether group.
7. The cleaning composition according to 5, wherein the thiazole compound having a carboxy hydrocarbon group is a compound represented by formula (T1).

(In the formula, ^D1 represents a single bond, an oxygen atom or a sulfur atom, ^D2 represents a carboxyalkyl group or a carboxyalkenyl group, ^D3 represents a substituent substituted on a benzene ring, and each independently represents a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and d represents the number of substituents and is an integer of 0 to 4.)
8. The cleaning composition according to claim 1, wherein the thiazole compound containing a carboxy hydrocarbon group contains 3-(2-benzothiazolylthio)propionic acid.
9. The cleaning composition according to any one of 1 to 8, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.
10. The cleaning composition according to 9, wherein the halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt.
11. The cleaning composition according to 10, wherein the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
12. The cleaning composition according to 11, wherein the tetra(hydrocarbon)ammonium fluoride includes at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride.
13. The cleaning composition according to any one of 1 to 12, wherein the polysiloxane-based adhesive remaining on the substrate is an adhesive residue of an adhesive layer obtained from an adhesive composition containing component (A) that cures by a hydrosilylation reaction.
14. A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate comprising a semiconductor substrate having a bump ball, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the resulting laminate; a third step of peeling off the semiconductor substrate after processing; and a fourth step of removing adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition, wherein the method for producing a processed semiconductor substrate is characterized in that the cleaning composition used is any one of the cleaning compositions 1 to 13.

By using the cleaning composition of the present invention, it is possible to easily clean substrates such as semiconductor substrates to which adhesive residues have adhered after peeling off a temporary bond formed by, for example, an adhesive layer obtained using a polysiloxane adhesive, particularly an adhesive layer that is a cured film obtained from a siloxane adhesive containing a polysiloxane component that cures by a hydrosilylation reaction, in a short time while suppressing corrosion of metals such as bump balls. Therefore, it is expected that semiconductor elements can be manufactured efficiently and with good quality.

The present invention will now be described in further detail.
The cleaning composition of the present invention contains a quaternary ammonium salt.
The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for this type of application.

Such quaternary ammonium cations typically include tetra(hydrocarbon)ammonium cations, while their counter anions include, but are not limited to, hydroxide ion (OH ⁻ ), halogen ions such as fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodide ion (I ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), and hexafluorophosphate ion (PF ₆ ⁻ ).

In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.
In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride.
Specific examples of the hydrocarbon group in the tetra(hydrocarbon)ammonium fluoride include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

In a preferred embodiment of the invention, the tetra(hydrocarbon)ammonium fluoride comprises a tetraalkylammonium fluoride.
Specific examples of tetraalkylammonium fluoride include, but are not limited to, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride), etc. Among these, tetrabutylammonium fluoride is preferred.

The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of a hydrate. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used alone or in combination of two or more.
The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the cleaning composition, but it is usually 0.1 to 30% by mass based on the cleaning composition.

The cleaning composition of the present invention contains a metal corrosion inhibitor comprising a thiazole compound containing a carboxy hydrocarbon group.
Examples of thiazole compounds containing such a carboxy hydrocarbon group include those containing at least one ring selected from a thiazole ring, an isothiazole ring, and a thiadiazole ring, and having one or more hydrocarbon groups containing one or more carboxy groups (—COOH).
The thiazole-based compound containing a carboxy hydrocarbon group is typically a thiazole derivative containing a carboxy hydrocarbon group, an isothiazole derivative containing a carboxy hydrocarbon group, or a thiadiazole derivative containing a carboxy hydrocarbon group.

The carboxyhydrocarbon group contained in the thiazole compound is not particularly limited as long as it is a hydrocarbon group containing one or more carboxy groups, but a carboxyalkyl group or a carboxyalkenyl group is preferred, and a carboxyalkyl group is more preferred from the viewpoint of realizing excellent cleaning ability and corrosion inhibition ability with better reproducibility.

Carboxyalkyl groups are alkyl groups substituted with one or more carboxy groups.
The alkyl group which substitutes the carboxy group may be linear, branched, or cyclic, and the number of carbon atoms therein is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, and a 3-methyl-n-pentyl group. Examples of the aryl group include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.
Of these, a methyl group is preferred.

Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl -cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, and other cycloalkyl groups; bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclodecyl group, and other bicycloalkyl groups, but are not limited to these.

Specific examples of carboxyalkyl groups include, but are not limited to, a carboxymethyl group, a dicarboxymethyl group, a tricarboxymethyl group, a 1-carboxyethyl group, a 2-carboxyethyl group, a 2,2-dicarboxyethyl group, a 2,2,2-tricarboxyethyl group, a 3-carboxypropyl group, a 4-carboxybutyl group, and a 5-carboxypentyl group.

Carboxyalkenyl groups are alkenyl groups substituted with one or more carboxy groups.
The alkenyl group which substitutes the carboxy group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

Specific examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl ethyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, a 1-cyclopentenyl group, a 2-cyclopentenyl group, a 3-cyclopentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, a 1-methyl-1-pentenyl group, a 1-methyl-2-pentenyl group, a 1-methyl-3-pentenyl group, a 1-methyl-4-pentenyl group, a 1-n-butylethenyl group, a 2-methyl-1-pentenyl group, a 2-methyl-2-pentenyl group, a 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1 ,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3 -dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group , 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, Examples of the cyclopentenyl group include, but are not limited to, cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

Specific examples of carboxyalkenyl groups include, but are not limited to, 2-hydroxyethenyl groups, 3-hydroxy-1-propenyl groups, and 3-hydroxy-2-propenyl groups.

In the carboxyalkyl group and the carboxyalkenyl group, the alkyl group and the alkenyl group substituted with the carboxy group are preferably linear or branched, more preferably linear, from the viewpoint of increasing solubility in organic solvents and realizing excellent cleaning ability and excellent corrosion inhibition ability with good reproducibility, and preferably at least one carboxy group is bonded to a terminal carbon atom of the linear or branched alkyl or alkenyl group. The terminal carbon atom means the carbon atom in the alkyl or alkenyl group that is farthest from the bond bonded to the heterocycle in the thiazole-based compound.

In a preferred embodiment of the present invention, the thiazole compound containing a carboxy hydrocarbon group contains a structure in which a thiazole ring, an isothiazole ring, or a thiadiazole ring is bonded to a carboxy hydrocarbon group directly or via an ether group or a thioether group, and from the viewpoint of realizing excellent cleaning ability and corrosion inhibition ability with better reproducibility, the thiazole compound preferably contains a structure in which a thiazole ring is bonded to a carboxy hydrocarbon group directly or via an ether group or a thioether group, and more preferably contains a structure in which a thiazole ring is bonded to a carboxy hydrocarbon group via a thioether group.

A preferred example of the thiazole compound containing a carboxy hydrocarbon group is a compound represented by the formula (T1).

In formula (T1), ^D1 represents a single bond, an oxygen atom or a sulfur atom, ^D2 represents a carboxyalkyl group or a carboxyalkenyl group, ^D3 represents a substituent (atom) substituted on a benzene ring, and each represents independently a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and d represents the number of substituents and is an integer of 0 to 4.

^D1 is preferably a sulfur atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group include the same as those mentioned above, and from the viewpoint of the solubility of the compound, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred.
Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and from the viewpoint of the solubility of the compound, the aryl group is preferred.
Examples of the alkoxy group include those composed of the above alkyl group and an oxygen atom, and from the viewpoint of the solubility of the compound, a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group are preferred.
The aryloxy group includes those composed of the above aryl group and an oxygen atom, and from the viewpoint of the solubility of the compound, a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group are preferred.
From the viewpoint of the availability of the compound and the solubility of the compound, d is preferably 3 or less, more preferably 2 or less, and even more preferably 1 or less.

Specific examples of thiazole compounds containing a carboxy hydrocarbon group include, but are not limited to, (2-benzothiazolylthio)acetic acid and 3-(2-benzothiazolylthio)propionic acid.

The amount of the metal corrosion inhibitor consisting of a thiazole compound containing a carboxy hydrocarbon group is not particularly limited as long as it dissolves in the organic solvent contained in the cleaning composition, but is usually 0.01 to 10 mass % relative to the cleaning composition.

The cleaning composition of the present invention may contain a metal corrosion inhibitor other than the metal corrosion inhibitor consisting of a thiazole compound containing a carboxy hydrocarbon group.

The cleaning composition of the present invention contains an organic solvent.
Such an organic solvent is not particularly limited as long as it is used for this type of application and can dissolve the quaternary ammonium salt and the metal corrosion inhibitor. From the viewpoint of reproducibly obtaining a cleaning composition having excellent detergency and from the viewpoint of satisfactorily dissolving the quaternary ammonium salt and the metal corrosion inhibitor and obtaining a cleaning composition having excellent uniformity, the organic solvent preferably contains one or more amide solvents.

An example of a preferred amide solvent is an acid amide derivative represented by the formula (Z).

In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, with an ethyl group being preferred. R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R ^A and R ^B are preferably a methyl group or an ethyl group.

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

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

Another example of a preferred amide solvent is a lactam compound represented by the formula (Y).

In the above formula (Y), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and specific examples of the alkylene group having 1 to 6 carbon atoms include, but are not limited to, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

Specific examples of the lactam compound represented by the above formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used alone or in combination of two or more.

In a preferred embodiment of the present invention, the lactam compound represented by the above formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

The cleaning composition of the present invention may contain one or more other organic solvents different from the above-mentioned amide compound.
Such other organic solvents are not particularly limited as long as they are used for this type of application and are compatible with the above-mentioned amide compound.

An example of a preferred other solvent is an alkylene glycol dialkyl ether.
Specific examples of alkylene glycol dialkyl ethers include, but are not limited to, ethylene glycol dimethyl ether (also referred to as dimethoxyethane, hereinafter), ethylene glycol diethyl ether (diethoxyethane), ethylene glycol dipropyl ethane (dipropoxyethane), ethylene glycol dibutyl ether (dibutoxyethane), propylene glycol dimethyl ether (dimethoxypropane), propylene glycol diethyl ether (diethoxypropane), propylene glycol dipropyl ether (dipropoxypropane), and the like.
The alkylene glycol dialkyl ethers may be used alone or in combination of two or more.

Another example of a preferable other solvent is an aromatic hydrocarbon compound, and a specific example thereof is an aromatic hydrocarbon compound represented by the formula (1).

In the above formula (1), specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
s represents the number of substituents R ¹⁰⁰ substituted on the benzene ring and is 2 or 3.

In a preferred embodiment of the present invention, the aromatic hydrocarbon compound represented by formula (1) is an aromatic hydrocarbon compound represented by formula (1-1) or (1-2).

R ¹⁰⁰ each independently represents an alkyl group having 1 to 6 carbon atoms, the total number of carbon atoms of the alkyl groups having 1 to 5 carbon atoms of the three R ¹⁰⁰ in formula (1-1) is 3 or more, and the total number of carbon atoms of the alkyl groups having 1 to 6 carbon atoms of the two R ¹⁰⁰ in formula (1-2) is 3 or more.

Specific examples of the aromatic hydrocarbon compound represented by formula (1) include, but are not limited to, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene (mesitylene), 4-ethyltoluene, 4-n-propyltoluene, 4-isopropyltoluene, 4-n-butyltoluene, 4-s-butyltoluene, 4-isobutyltoluene, and 4-t-butyltoluene.
Of these, mesitylene and 4-t-butyltoluene are preferable.

Another example of a preferred alternative solvent is a cyclic structure-containing ether compound. Examples of cyclic structure-containing ethers include cyclic ether compounds, cyclic alkyl chain alkyl ether compounds, cyclic alkyl branched alkyl ether compounds, and di(cyclic alkyl) ether compounds.

A cyclic ether compound is a compound in which at least one of the carbon atoms constituting the ring of a cyclic hydrocarbon compound is substituted with an oxygen atom.
Typically, examples of such cyclic ether compounds include epoxy compounds in which a linear, branched or cyclic saturated hydrocarbon compound is epoxidized (i.e., a three-membered ring is formed by two adjacent carbon atoms and an oxygen atom), and non-epoxy cyclic ether compounds in which a carbon atom constituting a ring of a cyclic hydrocarbon compound having 4 or more carbon atoms (excluding aromatic hydrocarbon compounds) is substituted with an oxygen atom (epoxy compounds are excluded; the same applies below). Among these, as such cyclic hydrocarbon compounds having 4 or more carbon atoms, cyclic saturated hydrocarbon compounds having 4 or more carbon atoms are preferred.

The number of carbon atoms in the epoxy compound is not particularly limited, but is usually 4 to 40, and preferably 6 to 12.
The number of epoxy groups is not particularly limited, but is usually 1 to 4, and preferably 1 or 2.

Specific examples of the epoxy compounds include epoxy linear or branched saturated hydrocarbon compounds such as 1,2-epoxy-n-butane, 1,2-epoxy-n-pentane, 1,2-epoxy-n-hexane, 1,2-epoxy-n-heptane, 1,2-epoxy-n-octane, 1,2-epoxy-n-nonane, 1,2-epoxy-n-decane, and 1,2-epoxy-n-eicosane, and epoxy cyclic saturated hydrocarbon compounds such as 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, 1,2-epoxycyclooctane, 1,2-epoxycyclononane, 1,2-epoxycyclodecane, and 1,2-epoxycycloeicosane, but are not limited to these.

The number of carbon atoms in the non-epoxy cyclic ether compound is not particularly limited, but is usually 3 to 40, and preferably 4 to 8.
The number of oxygen atoms (ether groups) is not particularly limited, but is usually 1 to 3, and preferably 1 or 2.

Specific examples of the cyclic ether compounds other than the above epoxy include oxacyclic saturated hydrocarbon compounds such as oxacyclobutane (oxetane), oxacyclopentane (tetrahydrofuran), and oxacyclohexane, and dioxacyclic saturated hydrocarbon compounds such as 1,3-dioxacyclopentane, 1,3-dioxacyclohexane (1,3-dioxane), and 1,4-dioxacyclohexane (1,4-dioxane), but are not limited to these.

The cyclic alkyl chain alkyl ether compound comprises a cyclic alkyl group, a chain alkyl group, and an ether group connecting the two, and the number of carbon atoms is not particularly limited, but is usually 4 to 40, and preferably 5 to 20.
The cyclic alkyl branched alkyl ether compound comprises a cyclic alkyl group, a branched alkyl group, and an ether group connecting the two, and the number of carbon atoms is not particularly limited, but is usually 6 to 40, and preferably 5 to 20.
A di(cyclic alkyl)ether compound comprises two cyclic alkyl groups and an ether group connecting them, and the number of carbon atoms therein is not particularly limited, but is usually 6 to 40, and preferably 10 to 20.
Among these, as the cyclic ether compounds other than epoxy, cyclic alkyl chain alkyl ether compounds and cyclic alkyl branched alkyl ether compounds are preferred, and cyclic alkyl chain alkyl ether compounds are more preferred.

The chain alkyl group is a group derived by removing a hydrogen atom from the terminal of a straight-chain aliphatic hydrocarbon, and the number of carbon atoms therein is not particularly limited, but is usually 1 to 40, and preferably 1 to 20.
Specific examples include, but are not limited to, a methyl group, an ethyl group, a 1-n-propyl group, a 1-n-butyl group, a 1-n-pentyl group, a 1-n-hexyl group, a 1-n-heptyl group, a 1-n-octyl group, a 1-n-nonyl group, and a 1-n-decyl group.

A branched alkyl group is a group derived by removing a hydrogen atom from a linear or branched aliphatic hydrocarbon, other than a chain alkyl group, and the number of carbon atoms therein is not particularly limited, but is usually 3 to 40, and preferably 3 to 40.
Specific examples thereof include, but are not limited to, an isopropyl group, an isobutyl group, a s-butyl group, and a t-butyl group.

A cyclic alkyl group is a group derived by removing a hydrogen atom on a carbon atom constituting a ring of a cyclic aliphatic hydrocarbon, and the number of carbon atoms therein is not particularly limited, but is usually 3 to 40, and preferably 5 to 20.
Specific examples thereof include monocycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, and cyclohexyl; and bicycloalkyl groups such as bicyclo[2.2.1]heptan-1-yl, bicyclo[2.2.1]heptan-2-yl, bicyclo[2.2.1]heptan-7-yl, bicyclo[2.2.2]octan-1-yl, bicyclo[2.2.2]octan-2-yl, and bicyclo[2.2.2]octan-7-yl, but are not limited to these.

Specific examples of cyclic alkyl chain alkyl ether compounds include, but are not limited to, cyclopentyl methyl ether (CPME), cyclopentyl ethyl ether, cyclopentyl propyl ether, cyclopentyl butyl ether, cyclohexyl methyl ether, cyclohexyl ethyl ether, cyclohexyl propyl ether, and cyclohexyl butyl ether.
Specific examples of the cyclic alkyl branched alkyl ether compound include, but are not limited to, cyclopentyl isopropyl ether, cyclopentyl t-butyl ether, and the like.
Specific examples of the di(cyclic alkyl) ether compound include, but are not limited to, dicyclopentyl ether, dicyclohexyl ether, and cyclopentylcyclohexyl ether.

The amount of the organic solvent other than the above-mentioned amide compound is usually determined appropriately to be 95% by mass or less of the solvent contained in the cleaning composition, so long as the components contained in the cleaning composition, such as the quaternary ammonium salt and the metal corrosion inhibitor, do not precipitate or separate and are uniformly mixed with the above-mentioned amide compound.

In the present invention, by using only an organic solvent as the solvent contained in the cleaning composition, it becomes possible to reduce the occurrence of metal contamination, metal corrosion, etc. caused by water and to suitably clean substrates with good reproducibility. Therefore, the cleaning composition of the present invention usually contains only an organic solvent as the solvent. Note that "only an organic solvent" means that only the organic solvent is intentionally used as the solvent, and does not deny the presence of water contained in the organic solvent or other components.
In other words, the cleaning composition of the present invention is characterized in that it is substantially free of water. Here, "substantially free of water" means that water is not blended, and does not exclude water as hydrates of other components or trace amounts of water mixed in with the components, as described above.
When the cleaning composition of the present invention is prepared using only an organic solvent as a solvent, the water content of the resulting cleaning composition cannot be generally defined because it varies depending on whether the organic solvent used has been dehydrated in advance, whether the organic solvent and solids used have high water absorption properties, whether the quaternary ammonium salt used is a hydrate, etc., but is usually less than 5 mass%, preferably less than 4 mass%, and more preferably less than 3 mass%. The water content can be calculated, for example, by the Karl Fischer method using a trace moisture analyzer CA-200 (manufactured by Mitsubishi Chemical Analytech Corp.).

The cleaning composition of the present invention is obtained by mixing the above-mentioned quaternary ammonium salt, the above-mentioned metal corrosion inhibitor, the above-mentioned organic solvent, and other components as necessary. The order of mixing the components can be any order as long as there are no problems such as precipitation or liquid separation that would prevent the object of the present invention from being achieved. That is, a part of all the components of the cleaning composition may be mixed in advance, and then the remaining components may be mixed, or all the components may be mixed at once. If necessary, the cleaning composition may be filtered, or the supernatant after mixing may be recovered while avoiding insoluble components, and used as a cleaning agent. Furthermore, if the components used are, for example, hygroscopic or deliquescent, all or part of the work of preparing the cleaning composition may be carried out under inert gas.

By using the cleaning composition of the present invention as described above, polysiloxane-based adhesive remaining on a semiconductor substrate such as a silicon wafer can be effectively removed. This not only enables the semiconductor substrate to be cleaned in a short time, but also makes it possible to suppress damage to metals such as bumps on the semiconductor substrate, which is expected to lead to the efficient production of good semiconductor elements.
Specifically, regarding the cleaning speed, when an adhesive layer obtained from an adhesive composition is contacted with the cleaning composition of the present invention for 5 minutes at room temperature (23° C.), the etching rate [μm/min] calculated by measuring the decrease in film thickness before and after contact and dividing the decrease by the cleaning time is usually 4.5 [μm/min] or more, in a preferred embodiment 5.0 [μm/min] or more, in a more preferred embodiment 5.5 [μm/min] or more, in an even more preferred embodiment 6.0 [μm/min] or more, and in an even more preferred embodiment 6.5 [μm/min] or more.
As for the cleaning durability, when 1 g of an adhesive solid obtained from the adhesive composition is contacted with 2 g of the cleaning composition of the present invention at room temperature (23° C.), the cleaning composition of the present invention usually dissolves most of the adhesive solid within 12 to 24 hours, and in a preferred embodiment, completely dissolves the adhesive solid within 2 to 12 hours, and in a more preferred embodiment, completely dissolves the adhesive solid within 1 to 2 hours.

By using the cleaning composition of the present invention described above, it is possible to effectively remove polysiloxane-based adhesives remaining on substrates such as semiconductor substrates, and as a result, not only can the substrate be cleaned in a short time, but also, if the substrate has bump balls, corrosion of the bump balls can be avoided or reduced, resulting in highly efficient and reliable substrate cleaning.

The cleaning composition of the present invention can be used to clean the surfaces of various substrates such as semiconductor substrates. The objects to be cleaned are not limited to silicon semiconductor substrates, but also include various substrates such as germanium substrates, gallium-arsenic substrates, gallium-phosphorus substrates, gallium-arsenic-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon substrates with silicon nitride films, silicon substrates with silicon oxide films, silicon substrates with polyimide films, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

For example, examples of the use of the cleaning composition of the present invention in semiconductor processes include use in a method for producing processed semiconductor substrates, such as thinned ones, used in semiconductor packaging techniques such as TSV.
Specifically, the cleaning composition of the present invention is used as the cleaning composition in a production method including: a first step of producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from the adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of peeling off the semiconductor substrate after processing; and a fourth step of removing adhesive residue remaining on the peeled semiconductor substrate with the cleaning composition.

As the adhesive composition used to form the adhesive layer in the first step, any of the various adhesive compositions described above can be used. However, the cleaning composition of the present invention is effective for removing an adhesive layer obtained from a polysiloxane-based adhesive, and is more effective for removing an adhesive layer obtained from a polysiloxane-based adhesive containing component (A) that cures by a hydrosilylation reaction.
Therefore, an example will be described below in which, when a semiconductor substrate is manufactured using an adhesive layer obtained by using a polysiloxane-based adhesive (adhesive composition), the adhesive layer is removed by using the cleaning composition of the present invention; however, the present invention is not limited thereto.

First, we will explain the first step of manufacturing a laminate comprising a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition.

In one embodiment, the first step includes a step of applying an adhesive composition to a surface of a semiconductor substrate or a supporting substrate to form an adhesive coating layer, and a step of bonding the semiconductor substrate and the supporting substrate via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the supporting substrate while performing at least one of a heat treatment and a decompression treatment to bond them together, and then performing a post-heat treatment to form a laminate.
In another embodiment, the first step includes, for example, a step of applying an adhesive composition to the circuit surface of a semiconductor substrate wafer and heating it to form an adhesive coating layer, a step of applying a release agent composition to the surface of a support substrate and heating it to form a release agent coating layer, and a step of bonding the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a decompression treatment, and then performing a post-heat treatment to form a laminate. Note that the adhesive composition is applied to the semiconductor substrate and the release agent composition is applied to the support substrate, respectively, and heated, but the adhesive composition and the release agent composition may be applied and heated sequentially to either one of the substrates, respectively.
In each of the above embodiments, the treatment conditions to be adopted, that is, the heat treatment, the reduced pressure treatment, or a combination of the two, are determined in consideration of various factors such as the type of adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the desired adhesive strength.

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

Examples of the wafer include, but are not limited to, silicon wafers and glass wafers having a diameter of about 300 mm and a thickness of about 770 μm.
In particular, the cleaning composition of the present invention can effectively clean a semiconductor substrate having bumps thereon while suppressing damage to the bumps by a cleaning method using the same.
Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps. Usually, the bump height is appropriately selected from the following conditions: about 1 to 200 μm, bump diameter is 1 to 200 μm, and bump pitch is 1 to 500 μm.
Specific examples of plated bumps include alloy plating mainly composed of Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps, but are not limited to these.

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

In a preferred embodiment, the polysiloxane-based adhesive (adhesive composition) comprises, as an adhesive component, a polyorganosiloxane component (A) that cures by a hydrosilylation reaction. In a more preferred embodiment, the polyorganosiloxane component (A) that cures by a hydrosilylation ^reaction comprises a ^polysiloxane ( ^A1 ) containing one or more units selected from the group consisting of siloxane units represented by _SiO2 (Q units), siloxane units represented by _R1R2R3SiO1 ^/ ₂ (M units), siloxane units represented by ^R4R5SiO2 _/ ² (D units), and siloxane units represented by R6SiO3/ ₂ (T units), ^{and a platinum} group metal catalyst (A2). and a polyorganosiloxane (a1) containing one or more units selected from the group consisting of siloxane units represented by SiO ₂ (Q" units), siloxane units represented by R ¹ "R ² "R 3 "SiO _1/2 (M' units), siloxane units represented by R ⁴ 'R ⁵ 'SiO _2/2 (D' units), and siloxane units represented by R ₆ 'SiO ^{3/2 (} T' units), and containing ^at least one unit selected from _the group consisting of M' units, D' units _, and T ^' units ^; and and a polyorganosiloxane _(a2 ) containing one or more units selected from the group consisting of siloxane units (T″ units) represented by the formula (I) and (II) and containing at least one unit selected from the group consisting of M″ units, D″ units and T″ units.

R ¹ to R ⁶ are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group, an alkenyl group, or a hydrogen atom.

R ¹ ' to R ⁶ ' are groups bonded to a silicon atom and each independently represents an alkyl group or an alkenyl group, provided that at least one of R ¹ ' to R ⁶ ' is an alkenyl group.

R ¹ ″ to R ⁶ ″ are groups or atoms bonded to the silicon atom and each independently represents an alkyl group or a hydrogen atom, provided that at least one of R ¹ ″ to R ⁶ ″ is a hydrogen atom.

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

Specific examples of alkyl groups include those mentioned above. Among them, methyl groups are preferred.

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

Specific examples of alkenyl groups include those mentioned above. Among them, ethenyl and 2-propenyl groups are preferred.

As described above, polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2), and the alkenyl groups contained in polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in polyorganosiloxane (a2) form a crosslinked structure through a hydrosilylation reaction caused by a platinum group metal catalyst (A2), and the crosslinked structure is cured.

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

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

In addition, when the polyorganosiloxane (a1) contains two or more types of polyorganosiloxane, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but are not limited to these.

Polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains at least one unit selected from the group consisting of M" units, D" units, and T" units. As polyorganosiloxane (a2), a combination of two or more polyorganosiloxanes satisfying these conditions may be used.

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

The polyorganosiloxane (a1) is composed of siloxane units having alkyl and/or alkenyl groups bonded to their silicon atoms, and the proportion of alkenyl groups in all of the substituents represented by R ¹ ' to R ⁶ ' is preferably 0.1 mol % to 50.0 mol %, more preferably 0.5 mol % to 30.0 mol %, and the remaining R ¹ ' to R ⁶ ' can be alkyl groups.

Polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and/or hydrogen atoms are bonded to the silicon atoms, and the proportion of hydrogen atoms in all the substituents and substituted atoms represented by R ¹ ″ to R ⁶ ″ is preferably 0.1 mol % to 50.0 mol %, more preferably 10.0 mol % to 40.0 mol %, and the remaining R ¹ ″ to R ⁶ ″ can be alkyl groups.

The polysiloxane (A1) contains polyorganosiloxane (a1) and polyorganosiloxane (a2), and in a preferred embodiment, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

The weight average molecular weight of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
The weight average molecular weight, number average molecular weight and dispersity in the present invention can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultiporeHZ-N, TSKgel SuperMultiporeHZ-H, manufactured by Tosoh Corporation), at a column temperature of 40° C., tetrahydrofuran as an eluent (elution solvent), a flow rate (flow velocity) of 0.35 mL/min, and polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is usually 10 to 1,000,000 (mPa·s), but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). Note that the viscosity in the present invention is a value measured with an E-type rotational viscometer at 25°C.

Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other to form a film by a hydrosilylation reaction. The mechanism of curing is therefore different from that via, for example, silanol groups, and therefore neither siloxane needs to contain silanol groups or functional groups that form silanol groups upon hydrolysis, such as alkyloxy groups.

In a preferred embodiment, the adhesive component (S) contains a platinum group metal catalyst (A2) together with the above-mentioned polysiloxane (A1).
Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl groups of the polyorganosiloxane (a1) and the Si-H groups of the polyorganosiloxane (a2).

Specific examples of platinum-based metal catalysts include platinum black, platinic chloride, chloroplatinic acid, a reaction product of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid with an olefin, platinum bisacetoacetate, and other platinum-based catalysts, but are not limited to these.
An example of a complex of platinum with an olefin is, but is not limited to, a complex of divinyltetramethyldisiloxane with platinum.
The amount of the platinum group metal catalyst (A2) is usually in the range of 1.0 to 50.0 ppm based on the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

The polyorganosiloxane component (A) may contain a polymerization inhibitor (A3) for the purpose of inhibiting the progress of the hydrosilylation reaction.
The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction. Specific examples include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol.
The amount of the polymerization inhibitor is usually 1000.0 ppm or more, based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), from the viewpoint of obtaining the effect, and 10000.0 ppm or less from the viewpoint of preventing excessive inhibition of the hydrosilylation reaction.

The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present invention, the resulting adhesive layer can be preferably peeled off with good reproducibility.
A typical example of such a release agent component (B) is a polyorganosiloxane, and specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, and phenyl group-containing polyorganosiloxanes.

The weight average molecular weight of the polyorganosiloxane, which is the release agent component (B), is usually 100,000 to 2,000,000, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. The dispersity is usually 1.0 to 10.0, but from the viewpoint of realizing the effects of the present invention with good reproducibility, it is preferably 1.5 to 5.0, more preferably 2.0 to 3.0. The weight average molecular weight and dispersity can be measured by the method described above.

The epoxy group-containing polyorganosiloxane may, for example, be one containing a siloxane unit ( ^D10 unit) represented by R ¹¹ R ¹² SiO _2/2 .

R ¹¹ is a group bonded to a silicon atom and represents an alkyl group, R ¹² is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group, and specific examples of the alkyl group include those mentioned above.

The epoxy group in the organic group containing an epoxy group may be an independent epoxy group that is not condensed with other rings, or it may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.

Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane is epoxy group-containing polydimethylsiloxane, but is not limited thereto.

The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D10 units), and may contain the above-mentioned Q units, M units and/or T units in addition to the ^D10 units.

In a preferred embodiment, specific examples of the epoxy group-containing polyorganosiloxane include polyorganosiloxanes consisting only of ^D10 units, polyorganosiloxanes containing ^D10 units and Q units, polyorganosiloxanes containing ^D10 units and M units, polyorganosiloxanes containing D10 units and T units, polyorganosiloxanes containing ^D10 units, Q units and M units, polyorganosiloxanes containing ^D10 units, M units and T units, polyorganosiloxanes containing ^D10 units, Q units, M units and T units, and polyorganosiloxanes containing ^D10 units, Q units, M units and T units.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5, and its weight average molecular weight is usually 1,500 to 500,000, but from the viewpoint of suppressing precipitation in the adhesive composition, it is preferably 100,000 or less.

Specific examples of epoxy group-containing polyorganosiloxanes include CMS-227 (manufactured by Gelest, weight average molecular weight 27,000) represented by formula (A-1), ECMS-327 (manufactured by Gelest, weight average molecular weight 28,800) represented by formula (A-2), KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 31,800) represented by formula (A-3), and KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 55,600) represented by formula (A-4). , Trade name KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 11,500) represented by formula (A-5), Trade name X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 2,400) represented by formula (A-6), Trade name BY16-839 (manufactured by Dow Corning Corporation, weight average molecular weight 51,700) represented by formula (A-7), Trade name ECMS-327 (manufactured by Gelest Co., Ltd., weight average molecular weight 28,800) represented by formula (A-8), and the like, but are not limited to these.

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

(m and n are the numbers of repeating units.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

(m and n are the numbers of repeating units.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

(m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

(m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ、ｎ及びｏはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

(m, n, and o are the numbers of repeating units. R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

(m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。Ｒは炭素数１～１０のアルキレン基である。）

(m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

（ｍ及びｎはそれぞれ繰り返し単位の数である。）

(m and n are the numbers of repeating units.)

Examples of the methyl group-containing polyorganosiloxane include those containing siloxane units represented by R ²¹⁰ R ²²⁰ SiO _2/2 (D ²⁰⁰ units), preferably those containing siloxane units represented by R ²¹ R ²¹ SiO _2/2 (D ²⁰ units).

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom and each independently represents an alkyl group, with at least one being a methyl group. Specific examples of the alkyl group include those listed above.
^R21 is a group bonded to a silicon atom and represents an alkyl group, specific examples of which include those mentioned above, with a methyl group being preferred as ^R21 .
A preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited thereto.

The methyl group-containing polyorganosiloxane contains the above-mentioned siloxane units (D ²⁰⁰ units or D ²⁰ units), but may contain the above-mentioned Q units, M units and/or T units in addition to the D ²⁰⁰ units and D ²⁰ units.

In one aspect, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane consisting of only D ²⁰⁰ units, a polyorganosiloxane containing D ²⁰⁰ units and Q units, a polyorganosiloxane containing D ²⁰⁰ units and M units, a polyorganosiloxane containing D ²⁰⁰ units and T units, a polyorganosiloxane containing D ²⁰⁰ units, Q units and M units, a polyorganosiloxane containing D ²⁰⁰ units, M units and T units, and a polyorganosiloxane containing D ²⁰⁰ units, Q units, M units and T units.

In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane consisting of only ^D20 units, a polyorganosiloxane containing ^D20 units and Q units, a polyorganosiloxane containing ^D20 units and M units, a polyorganosiloxane containing ^D20 units and T units, a polyorganosiloxane containing ^D20 units, Q units and M units, a polyorganosiloxane containing ^D20 units, M units and T units, and a polyorganosiloxane containing ^D20 units, Q units, M units and T units.

The viscosity of the methyl group-containing polyorganosiloxane is usually 1,000 to 2,000,000 mm ² /s, but preferably 10,000 to 1,000,000 mm ² /s. The methyl group-containing polyorganosiloxane is typically a dimethyl silicone oil made of polydimethylsiloxane. This viscosity value is indicated by kinematic viscosity, and centistokes (cSt) = mm ² /s. Kinematic viscosity can be measured with a kinematic viscometer. It can also be obtained by dividing the viscosity (mPa·s) by the density (g/cm ³ ). That is, it can be obtained from the viscosity and density measured by an E-type rotational viscometer at 25°C. It can be calculated from the formula kinematic viscosity (mm ² /s) = viscosity (mPa·s) / density (g/cm ³ ).

Specific examples of methyl group-containing polyorganosiloxanes include, but are not limited to, the WACKERSILICONE FLUID AK series manufactured by Wacker Chemical Co., Ltd., dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oil (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.

An example of the phenyl group-containing polyorganosiloxane is one containing a siloxane unit ( ^D30 unit) represented by R ³¹ R ³² SiO _2/2 .

R ³¹ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group. R ³² is a group bonded to a silicon atom and represents a phenyl group. Specific examples of the alkyl group include those mentioned above, but a methyl group is preferred.

The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane units ( ^D30 units), and may contain the above-mentioned Q units, M units and/or T units in addition to the ^D30 units.

In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include a polyorganosiloxane consisting of only ^D30 units, a polyorganosiloxane containing ^D30 units and Q units, a polyorganosiloxane containing ^D30 units and M units, a polyorganosiloxane containing ^D30 units and T units, a polyorganosiloxane containing ^D30 units, Q units and M units, a polyorganosiloxane containing ^D30 units, M units and T units, and a polyorganosiloxane containing ^D30 units, Q units, M units and T units.

The weight average molecular weight of the phenyl-containing polyorganosiloxane is usually 1,500 to 500,000, but is preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive composition.

Specific examples of the phenyl group-containing polyorganosiloxane include PMM-1043 (manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm ² /s) represented by formula (C-1), PMM-1025 (manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm ² /s) represented by formula (C-2), KF50-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm ² /s) represented by formula (C-3), and TSF431 (manufactured by MOMENTIVE, weight average molecular weight 1,800, viscosity 100 mm ² /s) represented by formula (C-4). Examples of such polyether ether copolymers include, but are not limited to, trade name TSF433 (manufactured by MOMENTIVE, weight average molecular weight 3,000, viscosity 450 mm ² /s) represented by formula (C-5), trade name PDM-0421 (manufactured by Gelest, Inc., weight average molecular weight 6,200, viscosity 100 mm ² /s) represented by formula (C-6), and trade name PDM-0821 (manufactured by Gelest, Inc., weight average molecular weight 8,600, viscosity 125 mm ² /s) represented by formula (C-7).

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

（ｍ及びｎは繰り返し単位の数を示す。）

(m and n represent the number of repeating units.)

In a preferred embodiment, the adhesive composition used in the present invention contains a release agent component (B) in addition to a polyorganosiloxane component (A) that cures by a hydrosilylation reaction, and in a more preferred embodiment, the release agent component (B) contains a polyorganosiloxane.

The adhesive composition used in the present invention can contain the adhesive component (S) and the release agent component (B) in any ratio. In consideration of the balance between adhesion and releasability, the ratio of component (S) to component (B) in mass ratio is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.
That is, when the polyorganosiloxane component (A) that cures by a hydrosilylation reaction is included, the ratio of component (A) to component (B) is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25, by mass.

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

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

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

The viscosity of the adhesive composition used in the present invention is usually 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s, at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of organic solvents used, their ratios, the concentrations of the film constituent components, etc., taking into consideration various factors such as the coating method used and the desired film thickness.

The adhesive composition used in the present invention can be prepared by mixing the adhesive component (S) with the release agent component (B), if used, and a solvent.
The mixing order is not particularly limited, but examples of a method for easily and reproducibly producing an adhesive composition include, but are not limited to, a method of dissolving the adhesive component (S) and the release agent component (B) in a solvent, or a method of dissolving a part of the adhesive component (S) and the release agent component (B) in a solvent and the rest in a solvent, and mixing the obtained solutions. Note that when preparing the adhesive composition, heating may be performed appropriately within a range that does not cause the components to decompose or change in quality.
In the present invention, for the purpose of removing foreign matter, the adhesive composition may be filtered using a sub-micrometer filter or the like during the production of the adhesive composition or after all of the components have been mixed.

The stripping agent composition includes a composition containing a stripping agent component used for this type of application.

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

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

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

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

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

The heat treatment is usually determined appropriately from the range of 20 to 150°C, taking into consideration the viewpoints of softening the adhesive coating layer to realize suitable bonding with the release agent coating layer, suitable curing of types of adhesive that do not sufficiently cure by heating when forming the adhesive coating layer, and suitable curing of the release agent coating layer. In particular, from the viewpoint of suppressing or avoiding excessive curing or unnecessary deterioration of the adhesive component or release agent component, the heating temperature is preferably 130°C or less, more preferably 90°C or less, and the heating time is usually 30 seconds or more, preferably 1 minute or more, from the viewpoint of reliably expressing adhesive and release properties, but is usually 10 minutes or less, preferably 5 minutes or less, from the viewpoint of suppressing deterioration of the adhesive layer and other members.

The reduced pressure treatment can be performed by exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an air pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

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

The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the layers between them and can firmly adhere them to each other, but is usually in the range of 10 to 1000 N.

The post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing speed, and is preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate, adhesive component, release agent component, etc. The heating time is usually 1 minute or more from the viewpoint of realizing suitable bonding of the wafer by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or less, preferably 120 minutes or less from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be performed using a hot plate, an oven, etc.
One of the purposes of the post-heat treatment is to more suitably cure the adhesive component (A).

Next, a second step of processing the semiconductor substrate of the laminate will be described.
An example of the processing applied to the laminate is processing of the back surface of the semiconductor substrate opposite to the circuit surface of the front surface, typically thinning the wafer by polishing the back surface of the wafer. Such a thinned wafer is used to form through-silicon vias (TSVs) and the like, and then the thinned wafer is peeled off from the support to form a wafer stack, which is then three-dimensionally mounted. In addition, before and after that, wafer back electrodes and the like are also formed. During the wafer thinning and TSV process, heat of 250 to 350° C. is applied while the wafer is attached to the support, and the adhesive layer contained in the laminate used in the present invention is usually heat resistant to that heat.
For example, a wafer with a diameter of 300 mm and a thickness of about 770 μm can be thinned to a thickness of about 80 to 4 μm by polishing the back surface opposite the circuit surface on the front surface.

Next, a third step of peeling off the semiconductor substrate made of the processed semiconductor substrate will be described.
The method of peeling off the laminate includes, but is not limited to, solvent peeling, laser peeling, mechanical peeling using a tool having a sharp part, peeling between a support and a wafer, etc. Peeling is usually performed after processing such as thinning.
In the third step, the adhesive is not necessarily completely attached to the supporting substrate and peeled off, and some of the adhesive may be left behind on the processed substrate. Therefore, in the fourth step, the surface of the substrate to which the residual adhesive is attached is cleaned with the cleaning composition of the present invention, whereby the adhesive residue on the substrate can be sufficiently removed.

Finally, the fourth step of removing adhesive residue remaining on the peeled semiconductor substrate by using a cleaning composition will be described.
The fourth step is a step of removing adhesive residue remaining on the semiconductor substrate after peeling using the cleaning composition of the present invention. Specifically, for example, the thinned substrate on which the adhesive remains is immersed in the cleaning composition of the present invention, and, if necessary, ultrasonic cleaning or other means are also used to remove the adhesive residue.
When ultrasonic cleaning is used, the conditions are appropriately determined taking into consideration the state of the surface of the substrate. Generally, the adhesive residue remaining on the substrate can be sufficiently removed by performing the cleaning treatment under conditions of 20 kHz to 5 MHz and 10 seconds to 30 minutes.

The manufacturing method of the processed substrate of the present invention includes the above-mentioned first to fourth steps, but may also include steps other than these. For example, in the fourth step, before cleaning with the cleaning composition of the present invention, adhesive residues may be removed by immersing the substrate in various solvents or by tape peeling, if necessary. In addition, the above-mentioned components and methodological elements related to the first to fourth steps may be modified in various ways without departing from the gist of the present invention.

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The following apparatuses were used in the present invention.
(1) Mixer (rotating/revolving mixer): Thinky Corporation Rotating/revolving mixer ARE-500
(2) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.
(3) Mixer: AS ONE Mix Rotor Variable 1-1186-12
(4) Mixer H: AS ONE heated rocking mixer HRM-1
(5) Contact-type film thickness meter: Tokyo Seimitsu Co., Ltd., wafer thickness measuring device WT-425

[1] Preparation of adhesive composition [Preparation Example 1]
A 600 mL stirring vessel dedicated to the planetary centrifugal mixer was charged with 150 g of a base polymer (manufactured by Wacker Chem.) consisting of a vinyl group-containing linear polydimethylsiloxane and a vinyl group-containing MQ resin having a viscosity of 200 mPa·s as (a1), 15.81 g of a SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chem.) having a viscosity of 100 mPa·s as (a2), and 0.17 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chem.) as (A3), and the mixture was stirred for 5 minutes with the planetary centrifugal mixer.
To the resulting mixture, 0.33 g of a platinum catalyst (manufactured by Wacker Chem.) as (A2) and 9.98 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chem.) having a viscosity of 1000 mPa·s as (a1) were stirred for 5 minutes in a planetary centrifugal mixer, and 0.52 g of the mixture obtained separately was added and stirred for 5 minutes in a planetary centrifugal mixer. The final mixture obtained was filtered through a 300 mesh nylon filter to obtain an adhesive composition.

[2] Preparation of cleaning composition [Example 1]
To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.), 0.5 g of 3-(2-benzothiazolylthio)propionic acid and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a cleaning composition.

[Comparative Example 1]
To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.), 0.5 g of succinic anhydride and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a cleaning composition.

[Comparative Example 2]
A cleaning composition was obtained by adding 0.5 g of adipic acid and 95 g of N,N-dimethylpropionamide to 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.) and stirring the mixture.

[Comparative Example 3]
To 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Ltd.), 0.5 g of glutaric acid and 95 g of N,N-dimethylpropionamide were added and stirred to obtain a cleaning composition.

[3] Performance evaluation of cleaning compositions Since a good cleaning composition needs to have a high cleaning speed that dissolves adhesive residues immediately after contacting them, the following evaluations were carried out. A higher cleaning speed is expected to result in more effective cleaning.
The etching rate was measured to evaluate the cleaning speed of the obtained cleaning composition. The adhesive composition obtained in Preparation Example 1 was applied to a 12-inch silicon wafer by a spin coater, and heated at 150°C for 15 minutes and then at 190°C for 10 minutes to form an adhesive layer (thickness 100 μm). The wafer with the film formed thereon was then cut into chips of 4 cm square, and the film thickness was measured using a contact film thickness meter.
The chips were then placed in a stainless steel petri dish with a diameter of 9 cm, 7 mL of the obtained cleaning composition was added, and the dish was covered with a lid. The dish was then placed on a stirrer H and stirred and washed for 5 minutes at 23° C. After washing, the chips were removed, washed with isopropanol and pure water, dried at 150° C. for 1 minute, and the film thickness was measured again with a contact film thickness meter. The film thickness reduction before and after washing was calculated, and the etching rate [μm/min] was calculated by dividing the reduction by the washing time, which was used as an index of cleaning power. The results are shown in Table 1.

Claims (14)

A cleaning composition used to remove adhesive residues, comprising a quaternary ammonium salt, a metal corrosion inhibitor consisting of a thiazole compound containing a carboxy hydrocarbon group, and an organic solvent. The cleaning composition according to claim 1, wherein the thiazole-based compound containing a carboxy hydrocarbon group is at least one selected from a thiazole derivative containing a carboxy hydrocarbon group, an isothiazole derivative containing a carboxy hydrocarbon group, and a thiadiazole derivative containing a carboxy hydrocarbon group. The cleaning composition according to claim 1 or 2, wherein the carboxy hydrocarbon group is a carboxy alkyl group or a carboxy alkenyl group. The cleaning composition according to claim 3, wherein the carboxy hydrocarbon group is a carboxy alkyl group. The cleaning composition according to claim 1, wherein the thiazole compound containing a carboxy hydrocarbon group has a structure in which a thiazole ring, an isothiazole ring, or a thiadiazole ring is bonded to a carboxy hydrocarbon group directly or via an ether group or a thioether group. The cleaning composition according to claim 5, wherein the thiazole compound containing a carboxy hydrocarbon group has a structure in which a thiazole ring and a carboxy hydrocarbon group are bonded directly or via an ether group or a thioether group. 6. The cleaning composition according to claim 5, wherein the thiazole compound containing a carboxy hydrocarbon group is a compound represented by formula (T1):

(In the formula, ^D1 represents a single bond, an oxygen atom or a sulfur atom, ^D2 represents a carboxyalkyl group or a carboxyalkenyl group, ^D3 represents a substituent substituted on a benzene ring, and each independently represents a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and d represents the number of substituents and is an integer of 0 to 4.) The cleaning composition according to claim 1, wherein the thiazole compound containing a carboxy hydrocarbon group contains 3-(2-benzothiazolylthio)propionic acid. The cleaning composition according to any one of claims 1 to 8, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt. The cleaning composition according to claim 9, wherein the halogen-containing quaternary ammonium salt is a fluorine-containing quaternary ammonium salt. The cleaning composition according to claim 10, wherein the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride. The cleaning composition according to claim 11, wherein the tetra(hydrocarbon)ammonium fluoride comprises at least one selected from the group consisting of tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride. 13. The cleaning composition according to any one of items 1 to 12 , wherein the adhesive residue comprises a polysiloxane-based adhesive remaining on a substrate, and is an adhesive residue of an adhesive layer obtained from an adhesive composition containing component (A) that cures by a hydrosilylation reaction. A method for producing a processed semiconductor substrate, comprising: a first step of producing a laminate including a semiconductor substrate having a bump ball, a support substrate, and an adhesive layer obtained from an adhesive composition; a second step of processing the semiconductor substrate of the obtained laminate; a third step of peeling off the semiconductor substrate after processing; and a fourth step of removing the adhesive residue remaining on the peeled semiconductor substrate with a cleaning composition, wherein the cleaning composition according to any one of claims 1 to 13 is used as the cleaning composition.