Method for cleaning semiconductor substrates and method for manufacturing processed semiconductor substrates

Abstract

To provide a cleaning method of a semiconductor substrate for suitably removing an adhesive layer on a semiconductor substrate after peeling of a temporary adhesive bond obtained by the adhesive layer, which is achieved by use of e.g. a siloxane-based adhesive, and a production method of a semiconductor device, which includes such a cleaning method.SOLUTION: A semiconductor substrate-cleaning method comprises the steps of: (A)swelling an adhesive layer on a semiconductor substrate by an organic solvent (S) to peel the adhesive layer from the semiconductor substrate; (B)removing the adhesive layer thus peeled; (C)removing a residue of the adhesive layer on the semiconductor substrate by use of a detergent composition containing a salt; and (D)rinsing the semiconductor substrate with a solvent (R) containing at least one kind selected from water and water-soluble solvent. The method does not comprise a step (N) of rinsing the semiconductor substrate with a solvent (N) between the steps (B) and (C).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for cleaning a semiconductor substrate and a method for manufacturing a processed semiconductor substrate. [Background technology]

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

[0003] Semiconductor wafers (referred to simply as wafers here) before thinning are bonded to a support in preparation for polishing with a polishing machine. This bond is called a temporary bond because it must be easily removable after polishing. This temporary bond must be easily removed from the support; applying a large force during removal can cause the thinned semiconductor wafer to break or deform, so it must be easily removed to prevent this. However, it is undesirable for the temporary bond to become dislodged or shifted due to the polishing stress during backside polishing. Therefore, the performance required for the temporary bond is to withstand the stress during polishing and be easily removed after polishing. For example, it must have high stress (strong adhesive strength) in the planar direction during polishing and low stress (weak adhesive strength) in the direction transverse to the planar direction during removal, i.e., the vertical direction. Furthermore, heat resistance is also required, as temperatures can reach temperatures of over 150°C during processing.

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

[0005] On the other hand, the semiconductor wafer is electrically connected to the semiconductor chip via bump balls made of a conductive material such as metal, and by using chips equipped with such bump balls, miniaturization of semiconductor packaging is being achieved. In this regard, bump balls made of metals such as copper and tin have poor corrosion resistance and are therefore subject to damage by cleaning compositions used to remove adhesive residues from supports and wafers (Patent Document 3). Therefore, one of the requirements for cleaning compositions and cleaning methods is to prevent the bump balls from corroding when cleaning substrates. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2014 / 092022 [Patent Document 2] U.S. Patent No. 6,818,608 [Patent Document 3] Korean Patent Publication No. 2018-0066550 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and aims to provide a method for cleaning a semiconductor substrate, for suitably removing an adhesive layer on a semiconductor substrate after peeling off a temporary adhesive layer obtained, for example, using a siloxane-based adhesive, and a method for manufacturing a processed semiconductor substrate that includes such a cleaning method. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that when a semiconductor substrate is cleaned using a cleaning method comprising the steps of: (A) swelling the adhesive layer on the semiconductor substrate with an organic solvent to peel the adhesive layer from the semiconductor substrate after peeling off a temporary adhesive layer formed using, for example, a siloxane-based adhesive; (B) removing the peeled adhesive layer; (C) removing adhesive layer residue on the semiconductor substrate using a cleaning composition containing a salt; and (D) rinsing the semiconductor substrate with a solvent (R) containing at least one selected from water and water-soluble solvents, by not including the step (N) of rinsing the semiconductor substrate with solvent (N) between steps (B) and (C), the residue on the substrate can be effectively removed, and the present invention has been completed.

[0009] That is, the present invention provides: 1. A step (A) of swelling an adhesive layer on a semiconductor substrate with an organic solvent (S) to peel off the adhesive layer from the semiconductor substrate; Step (B) of removing the peeled adhesive layer; (C) removing the adhesive layer residue on the semiconductor substrate using a cleaning composition containing a salt; and step (D) of rinsing the semiconductor substrate with a solvent (R) containing at least one selected from water and water-soluble solvents, a method for cleaning a semiconductor substrate, characterized in that a step (N) of rinsing the semiconductor substrate with a solvent (N) is not included between the step (B) and the step (C); 2. The method for cleaning a semiconductor substrate according to 1, wherein the water-soluble solvent contains at least one selected from alcohol, ether, ketone, nitrile, glycol, alkyl glycol, and dialkyl glycol. 3. The method for cleaning a semiconductor substrate according to 2, wherein the alcohol includes a lower alcohol. 4. The method for cleaning a semiconductor substrate according to 3, wherein the lower alcohol is selected from the group consisting of methanol, ethanol, propanol, and isopropanol. 5. The method for cleaning a semiconductor substrate according to any one of 1 to 4, wherein the organic solvent (S) contains at least one selected from the group consisting of an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ester compound, an ether compound, and a dimethyl silicone compound. 6. The method for cleaning a semiconductor substrate according to any one of 1 to 5, wherein the step (A) includes a step (A-1) of swelling the adhesive layer on the semiconductor substrate by continuously contacting the adhesive layer with an organic solvent (S) to peel the adhesive layer from the semiconductor substrate. 7. The method for cleaning a semiconductor substrate according to 6, wherein the step (A-1) includes a step (A-1-1) of swelling the adhesive layer on the semiconductor substrate by immersing the adhesive layer in an organic solvent (S) to peel the adhesive layer from the semiconductor substrate. 8. The method for cleaning a semiconductor substrate according to 6, wherein the step (A-1) includes a step (A-1-2) of swelling the adhesive layer on the semiconductor substrate by continuously supplying an organic solvent (S) onto the adhesive layer, and peeling the adhesive layer from the semiconductor substrate. 9. The method for cleaning a semiconductor substrate according to any one of 1 to 8, wherein the step (B) also serves as a step (K) of drying the semiconductor substrate, or the method includes a step (K) of drying the semiconductor substrate between the step (B) and the step (C). 10. The method for cleaning a semiconductor substrate according to any one of 1 to 9, wherein in the step (B), the peeled adhesive layer is removed by adsorption or suction, or by rotating the semiconductor substrate. 11. The method for cleaning a semiconductor substrate according to any one of 1 to 10, wherein the solvent (N) contains at least one selected from water and water-soluble solvents. 12. The method for cleaning a semiconductor substrate according to 11, wherein the water-soluble solvent contains at least one selected from alcohols, ethers, ketones, nitriles, glycols, alkyl glycols, and dialkyl glycols. 13. The method for cleaning a semiconductor substrate according to 12, wherein the alcohol comprises a lower alcohol. 14. The method for cleaning a semiconductor substrate according to 13, wherein the lower alcohol is selected from the group consisting of methanol, ethanol, propanol, and isopropanol. 15. A method for producing a processed semiconductor substrate, including the method for cleaning a semiconductor substrate according to any one of 1 to 14. to provide. [Effects of the Invention]

[0010] By using the semiconductor substrate cleaning method of the present invention, it is possible to effectively remove polysiloxane-based adhesive remaining on a substrate such as a silicon wafer, and not only can the substrate be cleaned in a short time, but also damage to the bumps on the substrate can be suppressed, which is expected to enable the efficient production of good semiconductor elements. DETAILED DESCRIPTION OF THE INVENTION

[0011] The method for cleaning a semiconductor substrate of the present invention includes a step (A) of swelling an adhesive layer on a semiconductor substrate with an organic solvent (S) and peeling it off from the semiconductor substrate.

[0012] The organic solvent (S) is used to swell the adhesive layer on the semiconductor substrate and peel it off from the semiconductor substrate, and specific examples thereof include, but are not limited to, chain or cyclic aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, chain or cyclic ester compounds, chain or cyclic ether compounds, dimethyl silicone compounds, etc.

[0013] Specific examples of the chain or cyclic aliphatic hydrocarbon compound include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isohexane, isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane, dimethylcyclohexanes, and trimethylcyclohexanes.

[0014] Specific examples of aromatic hydrocarbon compounds include, but are not limited to, p-menthane, limonene, toluene, xylene, trimethylbenzenes, p-cymene, and the like.

[0015] Specific examples of the chain or cyclic ester compound include, but are not limited to, ethyl acetate, propyl acetate, butyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, and propyl butyrate.

[0016] Specific examples of the chain or cyclic ether compound include, but are not limited to, propyl ether, dibutyl ether, hexadimethylsiloxane, and the like.

[0017] The organic solvent (S) preferably has low polarity as a whole molecule, a small molecular weight, and a small molecular surface area.

[0018] In a preferred embodiment of the present invention, the above step (A) includes a step (A-1) of swelling the adhesive layer on the semiconductor substrate by continuously contacting it with an organic solvent (S) and peeling it off from the semiconductor substrate. The method of continuously contacting the adhesive layer on the semiconductor substrate with the organic solvent (S) is not particularly limited, as long as the adhesive layer on the semiconductor substrate is in contact with the organic solvent (S) with temporal continuity. This temporal continuity includes not only cases in which the adhesive layer is constantly in contact with the organic solvent (S), but also cases in which, for example, the adhesive layer is brought into contact with the organic solvent for a certain period of time, the contact is stopped, and then the contact is resumed, or this is repeated. It also includes not only cases in which the entire adhesive layer on the semiconductor substrate is in contact with the organic solvent (S), but also cases in which only a portion of the adhesive layer is in contact with the organic solvent (S). However, from the viewpoint of achieving more effective cleaning with good reproducibility, a mode in which the adhesive layer on the semiconductor substrate is constantly in contact with the organic solvent (S) is preferred, and a mode in which the entire adhesive layer on the semiconductor substrate is in contact with the organic solvent (S) is also preferred.

[0019] Therefore, in a preferred embodiment of the present invention, the step (A-1) includes a step (A-1-1) of swelling the adhesive layer on the semiconductor substrate by immersing the adhesive layer in an organic solvent (S) and peeling it off from the semiconductor substrate, or a step (A-1-2) of swelling the adhesive layer on the semiconductor substrate by continuously supplying an organic solvent (S) onto the adhesive layer and peeling it off from the semiconductor substrate.

[0020] In order to immerse the adhesive layer on the semiconductor substrate in the organic solvent (S), for example, the semiconductor substrate with the adhesive layer attached thereto may be immersed in the organic solvent (S). The immersion time is not particularly limited as long as swelling of the adhesive layer occurs and the adhesive layer is peeled off from the semiconductor substrate, but is 5 seconds or more from the viewpoint of achieving more effective cleaning with good reproducibility, and 5 minutes or less from the viewpoint of process throughput.

[0021] When the adhesive layer on the semiconductor substrate is immersed in the organic solvent (S), the peeling of the adhesive layer may be promoted by moving the semiconductor substrate with the adhesive layer in the organic solvent (S), by convection of the organic solvent (S), by vibrating the organic solvent (S) with ultrasound, or the like.

[0022] In order to move the semiconductor substrate with the adhesive layer in the organic solvent (S), for example, a swinging washer, a paddle-type washer, or the like may be used. When such a washer is used, the stage on which the semiconductor substrate with the adhesive layer is placed moves up and down or left and right or rotates, so that the adhesive layer on the semiconductor substrate is subjected to relative convection, or the adhesive layer on the semiconductor substrate is subjected to convection generated by this movement or rotation, which not only causes the adhesive layer on the semiconductor substrate to swell but also promotes peeling of the adhesive layer from the semiconductor substrate.

[0023] In order to convect the organic solvent (S), in addition to the above-mentioned vibration washer or paddle type washer, for example, a convection washer may be used, which can typically realize a state in which the organic solvent (S) around the semiconductor substrate with the adhesive layer attached thereto is convected by an agitator while the semiconductor substrate is fixed on a stage or the like.

[0024] To vibrate the organic solvent (S) by ultrasonic waves, an ultrasonic cleaner or an ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.

[0025] To continuously supply the organic solvent (S) onto the adhesive layer on the semiconductor substrate, the organic solvent (S) can be continuously directed toward the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate faces upward, the organic solvent (S) can be continuously supplied over time from above (including diagonally above) the adhesive layer on the semiconductor substrate using a nozzle or the like of a cleaning device in the form of a rod or mist, preferably a rod, onto the adhesive layer on the semiconductor substrate. The continuous supply of the organic solvent (S) in this case does not only refer to a case where the organic solvent (S) is continuously supplied onto the adhesive layer on the semiconductor substrate, but also includes, for example, a case where the supply of the organic solvent (S) is continued for a certain period of time, then stopped, and then resumed, or a case where this process is repeated. However, from the viewpoint of achieving more effective cleaning with good reproducibility, it is preferable that the organic solvent (S) be continuously supplied onto the adhesive layer on the semiconductor substrate.

[0026] When the organic solvent (S) is supplied in a rod-like form onto the adhesive layer on the semiconductor substrate, the flow rate is usually 20 to 500 mL / min.

[0027] In one embodiment of the present invention, in order to ensure that the adhesive layer is constantly in contact with the organic solvent (S), the adhesive layer on the semiconductor substrate may be brought into contact with the vapor of the organic solvent (S), for example, using a steam cleaner.

[0028] The method for cleaning a semiconductor substrate of the present invention includes the step (B) of removing the peeled adhesive layer. The method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the semiconductor substrate, and when the semiconductor substrate with the adhesive layer is immersed in the organic solvent (S), the peeled adhesive layer may be removed without removing the semiconductor substrate from the organic solvent (S), or the peeled adhesive layer may be removed after removing the semiconductor substrate from the organic solvent (S). In this case, simply removing the semiconductor substrate from the organic solvent (S) may result in the peeled adhesive layer naturally remaining in the organic solvent (S), and most of it may be possible to remove it.

[0029] Specific examples of methods for removing the peeled adhesive layer include, but are not limited to, removing it by adsorption or suction using a device, blowing it off with gas such as an air gun, or removing it by centrifugal force caused by moving or rotating the semiconductor substrate up and down or left and right. Among these, the method of removing the peeled adhesive layer by rotating the semiconductor substrate using a spinner or the like and centrifugal force is preferred, since this method can also be used in the drying process described below, and the removal can be performed efficiently and effectively using centrifugal force.

[0030] In the present invention, when the organic solvent (S) used in the above-described step (A) has poor compatibility with the components of the cleaning composition used in the step (C) described below, the method for cleaning a semiconductor substrate of the present invention preferably includes, after the step (B) and before the step (C), a step (K) of drying the semiconductor substrate for the purpose of removing as much of the remaining organic solvent (S) as possible. Such drying may be performed by placing the semiconductor substrate in a dryer, blowing gas onto the semiconductor substrate with an air gun or the like, or rotating the semiconductor substrate, but is not limited to these methods. Among these, a method of rotating the semiconductor substrate using a spinner or the like is preferred, since this method can be performed at the same time as removing the peeled adhesive layer in step (B).

[0031] The method for cleaning a semiconductor substrate of the present invention includes a step (C) of removing adhesive layer residues on the semiconductor substrate using a cleaning agent composition containing a salt. By going through the above-mentioned steps (A) and (B), most of the adhesive layer on the semiconductor substrate is removed, but adhesive layer residue often remains on the semiconductor substrate, and this residue is removed in step (C).

[0032] Such a detergent composition is not particularly limited as long as it contains a salt used in this type of application, but typically includes a detergent composition containing an organic solvent and a quaternary ammonium salt. Such ammonium salts are composed of a quaternary ammonium cation and an anion, and are not particularly limited as long as they are used for this type of application.

[0033] The quaternary ammonium cation typically includes a tetra(hydrocarbon)ammonium cation. On the other hand, the anion paired with the quaternary ammonium cation is a hydroxide ion (OH - ); fluorine ion (F - ), chloride ions (Cl - ), bromide ion (Br - ), iodine ion (I - ) and other halogen ions; tetrafluoroborate ion (BF4 - ); Hexafluorophosphate ion (PF6 - ) and the like, but are not limited to these.

[0034] In the present invention, the quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt. In the quaternary ammonium salt, the halogen atom may be contained in either the cation or the anion, but is preferably contained in the anion.

[0035] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is a tetra(hydrocarbon)ammonium fluoride. Specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and aryl groups having 6 to 20 carbon atoms.

[0036] In a preferred embodiment of the present 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, etc. Among these, tetrabutylammonium fluoride (also called tetrabutylammonium fluoride) is preferred.

[0037] The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used in the form of hydrates. The quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may be used singly or in combination of two or more. The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the detergent composition, but is usually 0.1 to 30% by mass relative to the detergent composition.

[0038] The organic solvent contained in the cleaning composition used in the method for cleaning a semiconductor substrate of the present invention is not particularly limited as long as it is one that is used for this type of application, and examples thereof include amide compounds. More specifically, a preferred example is an acid amide derivative represented by formula (Z).

[0039] [ka]

[0040] In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, with an ethyl group being preferred. A and R B each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and a cyclobutyl group. Of these, R A and R B As the alkyl group, a methyl group or an ethyl group is preferred.

[0041] Examples of the acid amide derivative represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N,N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, etc. Of these, N,N-dimethylpropionamide is particularly preferred.

[0042] 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.

[0043] The amount of the amide compound is optional, but is usually 10% by mass or more based on the total solvent contained in the detergent composition. In one embodiment, from the viewpoint of improving the solubility of the quaternary ammonium salt and achieving higher detergency with good reproducibility, the amount is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0044] The cleaning composition used in the present invention may contain one or more other organic solvents different from the amide compound such as the acid amide derivative. Such other organic solvents are not particularly limited as long as they are used for this type of application, dissolve the quaternary ammonium salt, and are compatible with the amide compound.

[0045] An example of a preferred other organic solvent is alkylene glycol dialkyl ether.

[0046] Specific examples of alkylene glycol dialkyl ethers include, but are not limited to, ethylene glycol dimethyl ether (also called dimethoxyethane, the same applies 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 can be used alone or in combination of two or more.

[0047] An example of a preferable other organic solvent is an aromatic hydrocarbon compound, and a specific example thereof is an aromatic hydrocarbon compound represented by formula (1).

[0048] [ka]

[0049] 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 is a substituent R substituted on the benzene ring 100 represents the number of digits, and is either 2 or 3.

[0050] 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). [ka]

[0051] R 100 each independently represents an alkyl group having 1 to 6 carbon atoms, and the three R 100 The total number of carbon atoms in the alkyl groups having 1 to 6 carbon atoms is 3 or more, and the two R 100 The total number of carbon atoms in the alkyl groups having 1 to 6 carbon atoms is 3 or more.

[0052] 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. Among these, mesitylene and 4-t-butyltoluene are preferred.

[0053] An example of a preferred organic solvent is a cyclic structure-containing ether compound. Examples of the cyclic structure-containing ether include a cyclic ether compound, a cyclic alkyl chain alkyl ether compound, a cyclic alkyl branched alkyl ether compound, and a di(cyclic alkyl) ether compound. A cyclic ether compound is a cyclic hydrocarbon compound in which at least one of the carbon atoms constituting the ring is substituted with an oxygen atom. Typical examples include epoxy compounds in which a linear, branched, or cyclic saturated hydrocarbon compound is epoxidized (i.e., two adjacent carbon atoms and an oxygen atom form a three-membered ring), and cyclic ether compounds other than epoxy in which a carbon atom forming a ring of a cyclic hydrocarbon compound (excluding aromatic hydrocarbon compounds) having 4 or more carbon atoms is substituted with an oxygen atom (epoxy compounds are excluded; the same applies hereinafter). 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.

[0054] 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.

[0055] Specific examples of the epoxy compound include, but are not limited to, 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.

[0056] The number of carbon atoms in the cyclic ether compound other than epoxy 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.

[0057] Specific examples of the cyclic ether compound other than 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.

[0058] 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 consists of two cyclic alkyl groups and an ether group connecting them, and although the number of carbon atoms is not particularly limited, it 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.

[0059] A chain alkyl group is a group derived by removing a hydrogen atom from the terminal of a straight-chain aliphatic hydrocarbon, and although there are no particular limitations on the number of carbon atoms, it is usually 1 to 40, and preferably 1 to 20. Specific examples thereof 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.

[0060] 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 its carbon number is not particularly limited, but is usually 3 to 40, and preferably 3 to 20. Specific examples thereof include, but are not limited to, an isopropyl group, an isobutyl group, a s-butyl group, a t-butyl group, and the like.

[0061] A cyclic alkyl group is a group derived by removing a hydrogen atom from 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.

[0062] Specific examples of the cyclic alkyl chain alkyl ether compound 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 and cyclopentyl t-butyl ether. Specific examples of the di(cyclic alkyl) ether compound include, but are not limited to, dicyclopentyl ether, dicyclohexyl ether, and cyclopentyl cyclohexyl ether.

[0063] The cleaning composition that can be used in the method for cleaning semiconductor substrates of the present invention is obtained by mixing the above-mentioned quaternary ammonium salt or its hydrate, the above-mentioned organic solvent, and, if necessary, other components. Such hydrates include, but are not limited to, tetrabutylammonium fluoride trihydrate. The components of the detergent composition may be mixed in any order as long as this does not result in problems such as precipitation or separation of the composition. That is, some of the components of the detergent composition may be mixed in advance, and then the remaining components may be mixed, or all of the components may be mixed at once. If necessary, the detergent composition may be filtered, or the supernatant may be recovered after mixing, avoiding insoluble components, and used as the detergent composition. Furthermore, when the components used are, for example, hygroscopic or deliquescent, all or part of the steps for preparing the detergent composition may be carried out under an inert gas.

[0064] To remove adhesive layer residues from a semiconductor substrate using a cleaning composition, the cleaning composition may be brought into contact with the surface of the semiconductor substrate on which the adhesive layer residues are present. In this case, the cleaning composition may be supplied to the surface of the semiconductor substrate in the form of a mist or a rod, but a method of immersing the semiconductor substrate on which the adhesive layer residues are present in the cleaning composition is preferred because it allows the cleaning composition to be brought into contact with the surface of the semiconductor substrate simply and efficiently.

[0065] The immersion time of a semiconductor substrate having adhesive layer residue in the cleaning composition is usually 15 seconds or more, preferably 20 seconds or more, more preferably 2 minutes or more from the viewpoint of reliably removing the adhesive layer residue, and is usually 4 minutes or less, preferably 3 minutes or less from the viewpoint of minimizing the contact time between the cleaning composition and the bumps of the semiconductor substrate and suppressing damage to the bumps. After immersion in the cleaning composition, the semiconductor substrate is removed from the cleaning composition.

[0066] The method for cleaning a semiconductor substrate of the present invention includes a step (D) of rinsing the semiconductor substrate with a solvent (R) containing at least one solvent selected from water and water-soluble solvents. The main purpose of step (D) is to remove the cleaning composition used in step (C) from the semiconductor substrate and to prevent the components of the cleaning composition from being deposited on the semiconductor substrate and damage to the bumps of the semiconductor substrate caused by the cleaning composition. Rinsing with a solvent (R) containing at least one selected from water and water-soluble solvents allows the cleaning composition to be removed efficiently and effectively from the semiconductor substrate, particularly without damaging the bumps of the semiconductor substrate.

[0067] Specific examples of water-soluble solvents used in rinsing include, but are not limited to, alcohols, ethers, ketones, nitriles, glycols, alkyl glycols, dialkyl glycols, etc. These can be used alone or in combination of two or more.

[0068] The alcohol is preferably a lower alcohol having 1 to 5 carbon atoms such as methanol, ethanol, propanol, isopropanol, or butanol, and among these, isopropanol is preferred.

[0069] Specific examples of ethers include, but are not limited to, oxacyclobutane (oxetane), oxacyclopentane (tetrahydrofuran), oxacyclohexane, 1,3-dioxacyclopentane, 1,3-dioxacyclohexane (1,3-dioxane), 1,4-dioxacyclohexane (1,4-dioxane), and the like.

[0070] Specific examples of ketones include, but are not limited to, acetone, acetonylacetone, and the like.

[0071] Specific examples of nitriles include, but are not limited to, acetonitrile, 3-methoxypropionitrile, 3-ethoxypropionitrile, and the like.

[0072] Specific examples of glycols include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, 1,2-butanediol, 2,3-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.

[0073] Specific examples of alkyl glycols include ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, diethylene glycol monopropyl ether (propyl carbitol), diethylene glycol monohexyl ether (hexyl carbitol), 2-ethylhexyl carbitol, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl ether, diethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, and 2-phenoxyethanol, but are not limited to these.

[0074] Specific examples of dialkyl glycols include glycol diether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether, but are not limited to these.

[0075] To rinse a semiconductor substrate with water and / or a water-soluble solvent, the surface of the semiconductor substrate that has been in contact with the cleaning composition may be brought into contact with the water and / or the water-soluble solvent. In this case, the water and / or the water-soluble solvent may be supplied in the form of a mist or a rod toward the surface of the semiconductor substrate. However, the method of immersing the semiconductor substrate in water and / or the water-soluble solvent is preferred because it allows the water and / or the water-soluble solvent to be brought into contact with the surface of the semiconductor substrate simply and efficiently. Furthermore, by immersing the semiconductor substrate in water and / or a water-soluble solvent, both sides of the semiconductor substrate can be rinsed simultaneously. Therefore, when the cleaning composition comes into contact with both sides of the semiconductor substrate, efficient and effective rinsing can be expected.

[0076] The immersion time of the semiconductor substrate in water and / or the water-soluble solvent is about 30 seconds to 5 minutes, but from the viewpoint of ensuring complete removal of the cleaning composition, it is usually 1 minute or more, preferably 3 minutes or more. After the immersion, the semiconductor substrate is removed from the water and / or the water-soluble solvent. When water and / or a water-soluble solvent is supplied to the surface of the semiconductor substrate in the form of a mist or a rod, the supply time is about 30 seconds to 5 minutes, but from the viewpoint of completely removing the cleaning composition, the supply time is usually 1 minute or more, preferably 3 minutes or more. In this case, when the cleaning composition comes into contact with both surfaces of the semiconductor substrate, the water and / or a water-soluble solvent is supplied to both surfaces of the semiconductor substrate simultaneously or sequentially.

[0077] From the viewpoint of improving the handleability of the substrate and preventing the adhesion of impurities to the substrate, the substrate is usually dried after rinsing with water and / or a water-soluble solvent. Drying may be performed by placing the semiconductor substrate in a dryer, blowing gas onto the semiconductor substrate with an air gun or the like, or rotating the semiconductor substrate, but is not limited to these methods. Among these, a method of rotating the semiconductor substrate using a spinner or the like is preferred because it allows the substrate to be dried simply and effectively.

[0078] The method for cleaning a semiconductor substrate of the present invention does not include a step (N) of rinsing the semiconductor substrate with a solvent (N) between the above steps (B) and (C). Here, not including a step of rinsing with a solvent (N) means that after performing step (B) and before removing the adhesive layer residue in step (C), rinsing with any solvent is not performed. Therefore, the solvent (N) does not include the cleaning composition containing the salt used in step (C), but includes the organic solvent (S) and the solvent (R). That is, after the organic solvent (S) used in step (A) is removed from the semiconductor substrate, it is important not to contact the semiconductor substrate with another solvent (N) before contacting the semiconductor substrate with the cleaning composition containing the salt used in step (C). If a step (N) of rinsing the semiconductor substrate with a solvent (N) is included between the steps (B) and (C), a problem occurs in that the adhesive layer residue cannot be effectively removed in the step (C). The reason for this is presumably that the peeled adhesive layer re-adheres to the semiconductor substrate when treated with the solvent (N) in the step (N).

[0079] By using the semiconductor substrate cleaning method of the present invention as described above, it is possible to effectively remove polysiloxane-based adhesive remaining on a substrate such as a silicon wafer, and not only can the substrate be cleaned in a short time, but damage to the bumps on the substrate can also be suppressed, which is expected to enable the efficient production of good semiconductor elements.

[0080] The semiconductor substrate to be cleaned by the cleaning method of the present invention is not limited to silicon semiconductor substrates, but also includes various substrates such as germanium substrates, gallium-arsenide substrates, gallium-phosphorus substrates, gallium-arsenide-aluminum substrates, aluminum-plated silicon substrates, copper-plated silicon substrates, silver-plated silicon substrates, gold-plated silicon substrates, titanium-plated silicon substrates, silicon nitride film-formed silicon substrates, silicon oxide film-formed silicon substrates, polyimide film-formed silicon substrates, glass substrates, quartz substrates, liquid crystal substrates, and organic EL substrates.

[0081] An example of the use of the cleaning method for semiconductor substrates in semiconductor processes is in a manufacturing method for thinned substrates used in semiconductor packaging techniques such as TSV. Specifically, the method for producing a semiconductor substrate that has been processed, such as thinned, includes a first step of producing a laminate comprising a semiconductor substrate, 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 separating the processed semiconductor substrate and adhesive layer from the support substrate; and a fourth step of removing the adhesive layer from the processed semiconductor substrate and cleaning the processed semiconductor substrate, in which the semiconductor substrate cleaning method of the present invention is used in the fourth step.

[0082] The adhesive composition used to form the adhesive layer in the first step is typically at least one adhesive selected from polysiloxane-based, acrylic resin-based, epoxy resin-based, polyamide-based, polystyrene-based, polyimide-based, and phenolic resin-based adhesives. However, the cleaning composition of the present invention is particularly effective for cleaning polysiloxane-based adhesives. In particular, the cleaning composition of the present invention is effective for removing adhesive residues from polysiloxane-based adhesives containing component (A) that cures via a hydrosilylation reaction. Therefore, the following describes a method for producing a thinned substrate using a polysiloxane adhesive (adhesive composition) containing component (A) that cures via a hydrosilylation reaction and the cleaning composition of the present invention, but the present invention is not limited thereto.

[0083] First, the first step of producing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described. The component (A) contained in the adhesive composition that cures by a hydrosilylation reaction is, for example, a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 Siloxane unit (M unit) represented by R 4 R 5 SiO 2 / 2 Siloxane units (D units) represented by the formula 6 SiO 3 / 2 and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) contains one or more units selected from the group consisting of siloxane units (Q' units) represented by SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 Siloxane unit (M' unit) represented by R 4 'R 5 'SiO 2 / 2 Siloxane units (D' units) represented by the formula: and R 6 'SiO 3 / 2and a polyorganosiloxane (a1) containing one or more units selected from the group consisting of siloxane units (T' units) represented by the following formula: and at least one unit selected from the group consisting of the M' units, D' units and T' units; a polyorganosiloxane (a2) containing siloxane units (Q" units) represented by the formula: 1 "R 2 "R 3 "SiO 1 / 2 Siloxane unit (M" unit) represented by R 4 "R 5 "SiO 2 / 2 Siloxane units (D" units) represented by and R 6 "SiO 3 / 2 and a polyorganosiloxane (a2) containing one or more units selected from the group consisting of siloxane units (T" units) represented by the following formula: and containing at least one unit selected from the group consisting of the M" units, D" units and T" units.

[0084] R 1 ~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 '~R 6 R ' is a group bonded to a silicon atom, and each independently represents an alkyl group or an alkenyl group. 1 '~R 6 At least one of the groups is an alkenyl group. R 1 ”~R 6 " are groups or atoms bonded to the silicon atom, and each independently represents an alkyl group or a hydrogen atom, but R 1 ”~R 6 At least one of " is a hydrogen atom.

[0085] The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0086] Specific examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, and a 3-methyl-n-pentyl group. Examples of such alkyl groups include, but are not limited to, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group. Of these, a methyl group is preferred.

[0087] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4-dimethyl cycloalkyl groups such as 1-n-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, and 2-ethyl-3-methyl-cyclopropyl group; and bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group, but are not limited to these.

[0088] The alkenyl group may be either linear or branched, and the number of carbon atoms therein is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0089] Specific examples of the alkenyl group 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-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2- propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1- pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 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- Examples of the alkyl group include, but are not limited to, a 2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. Of these, ethenyl and 2-propenyl groups are preferred.

[0090] As described above, the polysiloxane (A1) contains the polyorganosiloxane (a1) and the polyorganosiloxane (a2), and the alkenyl groups contained in the polyorganosiloxane (a1) and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2) undergo a hydrosilylation reaction in the presence of a platinum group metal catalyst (A2) to form a crosslinked structure and cure.

[0091] The polyorganosiloxane (a1) contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and also contains at least one unit selected from the group consisting of M' units, D' units, and T' units. As the polyorganosiloxane (a1), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0092] 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).

[0093] Furthermore, when two or more types of polyorganosiloxanes included in polyorganosiloxane (a1) are contained, 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.

[0094] The polyorganosiloxane (a2) contains one or more units selected from the group consisting of Q″ units, M″ units, D″ units, and T″ units, and also contains at least one unit selected from the group consisting of M″ units, D″ units, and T″ units. As the polyorganosiloxane (a2), two or more polyorganosiloxanes satisfying these conditions may be used in combination.

[0095] 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).

[0096] The polyorganosiloxane (a1) is composed of siloxane units in which alkyl and / or alkenyl groups are bonded to the silicon atoms thereof, and R1 '~R 6 The proportion of alkenyl groups in all the substituents represented by R 1 '~R 6 ' can be an alkyl group.

[0097] The polyorganosiloxane (a2) is composed of siloxane units in which alkyl groups and / or hydrogen atoms are bonded to the silicon atoms. 1 ”~R 6 The proportion of hydrogen atoms in all the substituents and substituted atoms represented by R is preferably 0.1 mol % to 50.0 mol %, more preferably 10.0 mol % to 40.0 mol %, and the remaining R 1 ”~R 6 " can be an alkyl group.

[0098] The polysiloxane (A1) contains a polyorganosiloxane (a1) and a polyorganosiloxane (a2). In a preferred embodiment of the present invention, the molar ratio of the alkenyl groups contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bonds contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0099] The weight average molecular weight of each of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) is usually 500 to 1,000,000, and preferably 5,000 to 50,000.

[0100] The weight-average molecular weight can be measured, for example, using a GPC apparatus (EcoSEC, HLC-8320GPC, manufactured by Tosoh Corporation) and a GPC column (Shodex (registered trademark), KF-803L, KF-802, and KF-801, manufactured by Showa Denko K.K.), setting the column temperature to 40°C, using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) to 1.0 mL / min, and using polystyrene (manufactured by Sigma-Aldrich) as a standard sample.

[0101] The polyorganosiloxane (a1) and polyorganosiloxane (a2) contained in this adhesive composition react with each other by hydrosilylation to form a cured film. Therefore, the curing mechanism is different from that via, for example, silanol groups, and therefore neither siloxane needs to contain a functional group that forms a silanol group upon hydrolysis, such as a silanol group or an alkyloxy group.

[0102] Component (A) includes a platinum group metal catalyst (A2). 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).

[0103] Specific examples of platinum-based metal catalysts include, but are not limited to, platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid with monohydric alcohols, complexes of chloroplatinic acid with olefins, and platinum bisacetoacetate. Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.

[0104] 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).

[0105] Component (A) may contain a polymerization inhibitor (A3). That is, by including a polymerization inhibitor in the adhesive composition, it becomes possible to suitably control curing due to heating during lamination, and it is possible to reproducibly obtain an adhesive composition that gives an adhesive layer with excellent adhesion and peelability.

[0106] The polymerization inhibitor (A3) is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction. Specific examples include, but are not limited to, alkynylalkyl alcohols which may be substituted with an aryl group, such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0107] The amount of the polymerization inhibitor (A3) is usually 1000.0 ppm or more relative to the polyorganosiloxane (a1) and the polyorganosiloxane (a2) in order to obtain its effect, and 10000.0 ppm or less in order to prevent excessive inhibition of the hydrosilylation reaction.

[0108] The adhesive composition may contain component (B) containing at least one selected from the group consisting of a component containing an epoxy-modified polyorganosiloxane, a component containing a methyl group-containing polyorganosiloxane, and a component containing a phenyl group-containing polyorganosiloxane. By including such component (B) in the adhesive composition, the resulting adhesive layer can be suitably peeled with good reproducibility.

[0109] Examples of epoxy-modified polyorganosiloxane include R 11 R 12 SiO 2 / 2 The siloxane unit (D 10 Examples include those containing units.

[0110] R 11 is a group bonded to a silicon atom and represents an alkyl group, and 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 listed above.

[0111] Furthermore, 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 may be an epoxy group that forms a condensed ring with other rings, such as a 1,2-epoxycyclohexyl group.

[0112] Specific examples of organic groups containing an epoxy group include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.

[0113] In the present invention, a preferred example of the epoxy-modified polyorganosiloxane is epoxy-modified polydimethylsiloxane, but is not limited thereto.

[0114] The epoxy-modified polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 10 units), but D 10 In addition to the units, the above Q units, M units and / or T units may be contained.

[0115] In a preferred embodiment, specific examples of the epoxy-modified polyorganosiloxane include D 10 Polyorganosiloxane consisting of only units, D 10 polyorganosiloxanes containing D units and Q units; 10 Polyorganosiloxanes containing D units and M units, 10 Polyorganosiloxanes containing D units and T units, 10 polyorganosiloxanes containing units, Q units and M units, D 10 Polyorganosiloxanes containing units, M units and T units, D 10 Examples of suitable organosiloxanes include polyorganosiloxanes containing Q units, M units, and T units.

[0116] The epoxy-modified polyorganosiloxane is preferably an epoxy-modified 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.

[0117] Specific examples of epoxy-modified polyorganosiloxanes include CMS-227 (manufactured by Gelest Co., Ltd., weight-average molecular weight 27,000) represented by formula (A-1), ECMS-327 (manufactured by Gelest Co., Ltd., 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). Examples of such an alkyl acrylate copolymer include, but are not limited to, KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 11,500) represented by formula (A-5), X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 2,400) represented by formula (A-6), BY16-839 (manufactured by Dow Corning Corporation, weight-average molecular weight 51,700) represented by formula (A-7), and ECMS-327 (manufactured by Gelest Pharmaceuticals, weight-average molecular weight 28,800) represented by formula (A-8).

[0118] [ka] (m and n are the numbers of repeating units, respectively.)

[0119] [ka] (m and n are the numbers of repeating units, respectively.)

[0120] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0121] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0122] [ka] (m, n, and o each represent the number of repeating units. R represents an alkylene group having 1 to 10 carbon atoms.)

[0123] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0124] [ka] (m and n are the numbers of repeating units, and R is an alkylene group having 1 to 10 carbon atoms.)

[0125] [ka] (m and n are the numbers of repeating units, respectively.)

[0126] Examples of the methyl group-containing polyorganosiloxane include R 210 R 220 SiO 2 / 2 The siloxane unit (D 200 units), preferably R 21 R 21 SiO 2 / 2 The siloxane unit (D 20 Examples include those containing units.

[0127] 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. R 21 is a group bonded to a silicon atom, and represents an alkyl group. Specific examples of the alkyl group include those listed above. 21 As the alkyl group, a methyl group is preferred.

[0128] A preferred example of the methyl group-containing polyorganosiloxane is polydimethylsiloxane, but is not limited to this.

[0129] The methyl group-containing polyorganosiloxane is a polyorganosiloxane having the above-mentioned siloxane unit (D 200 Unit or D 20 units), but D 200 Units and D 20 In addition to the units, the above Q units, M units and / or T units may be contained.

[0130] In one embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include D 200 Polyorganosiloxane consisting of only units, D 200 polyorganosiloxanes containing D units and Q units; 200 Polyorganosiloxanes containing D units and M units, 200 Polyorganosiloxanes containing D units and T units, 200 polyorganosiloxanes containing units, Q units and M units, D 200 Polyorganosiloxanes containing units, M units and T units, D 200 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0131] In a preferred embodiment, specific examples of the methyl group-containing polyorganosiloxane include D 20 Polyorganosiloxane consisting of only units, D 20 polyorganosiloxanes containing D units and Q units; 20 Polyorganosiloxanes containing D units and M units, 20 Polyorganosiloxanes containing D units and T units, 20 polyorganosiloxanes containing units, Q units and M units, D 20 Polyorganosiloxanes containing units, M units and T units, D 20 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0132] The viscosity of 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. Methyl group-containing polyorganosiloxane is typically a dimethyl silicone oil made of polydimethylsiloxane. This viscosity value is expressed as kinematic viscosity, and is expressed as centistokes (cSt) = mm 2 / s. Kinematic viscosity can be measured using a kinematic viscometer. Viscosity (mPa s) can also be converted to density (g / cm 3 ) can also be calculated by dividing by the viscosity measured at 25°C using an E-type rotational viscometer and the density. 2 / s) = viscosity (mPa s) / density (g / cm 3 ) can be calculated from the formula:

[0133] Specific examples of methyl group-containing polyorganosiloxanes include the WACKER SILICONE FLUID AK series manufactured by Wacker Chemie, dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) manufactured by Shin-Etsu Chemical Co., Ltd., and cyclic dimethyl silicone oil (KF-995), but are not limited to these.

[0134] Examples of the phenyl group-containing polyorganosiloxane include R 31 R 32 SiO 2 / 2 The siloxane unit (D 30 Examples include those containing units.

[0135] R 31 is a group bonded to a silicon atom and represents a phenyl group or an alkyl group; R 32 is a group bonded to a silicon atom, and represents a phenyl group. Specific examples of the alkyl group include those listed above, with a methyl group being preferred.

[0136] The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit (D 30 units), but D 30 In addition to the units, the above Q units, M units and / or T units may be contained.

[0137] In a preferred embodiment, specific examples of the phenyl group-containing polyorganosiloxane include D 30 Polyorganosiloxane consisting of only units, D 30 polyorganosiloxanes containing D units and Q units; 30 Polyorganosiloxanes containing D units and M units, 30 Polyorganosiloxanes containing D units and T units, 30 polyorganosiloxanes containing units, Q units and M units, D 30 Polyorganosiloxanes containing units, M units and T units, D 30 Examples of suitable polyorganosiloxanes include polyorganosiloxanes containing Q, M, and T units.

[0138] The weight average molecular weight of the phenyl group-containing polyorganosiloxane 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.

[0139] A specific example of the phenyl group-containing polyorganosiloxane is PMM-1043 (trade name, manufactured by Gelest, Inc., weight average molecular weight 67,000, viscosity 30,000 mm), represented by formula (C-1). 2 / s), and PMM-1025 (trade name, manufactured by Gelest, Inc., weight average molecular weight 25,200, viscosity 500 mm 2 / s), and the trade name KF50-3000CS (manufactured by Shin-Etsu Chemical Co., Ltd., weight average molecular weight 39,400, viscosity 3000 mm represented by formula (C-3). 2 / s), and the product name TSF431 (manufactured by MOMENTIVE Co., Ltd., weight average molecular weight 1,800, viscosity 100 mm 2 / s), and the product name TSF433 (manufactured by MOMENTIVE Co., Ltd., weight average molecular weight 3,000, viscosity 450 mm2 / s), and PDM-0421 (trade name, manufactured by Gelest, Inc., weight average molecular weight 6,200, viscosity 100 mm) represented by formula (C-6). 2 / s), and PDM-0821 (trade name, manufactured by Gelest, Inc., weight average molecular weight 8,600, viscosity 125 mm 2 / s), but are not limited to these.

[0140] [ka] (m and n represent the number of repeating units.)

[0141] [ka] (m and n represent the number of repeating units.)

[0142] [ka] (m and n represent the number of repeating units.)

[0143] [ka] (m and n represent the number of repeating units.)

[0144] [ka] (m and n represent the number of repeating units.)

[0145] [ka] (m and n represent the number of repeating units.)

[0146] [ka] (m and n represent the number of repeating units.)

[0147] The polysiloxane adhesive composition may contain component (A) and component (B) in any ratio. However, taking into consideration the balance between adhesiveness and releasability, the ratio of component (A) to component (B) by mass is preferably 99.995:0.005 to 30:70, and more preferably 99.9:0.1 to 75:25.

[0148] Such adhesive compositions may contain a solvent for purposes such as adjusting viscosity, and specific examples of such a solvent include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, and ketones.

[0149] More specific examples include, but are not limited to, hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, etc. These solvents can be used alone or in combination of two or more.

[0150] When such an adhesive composition contains a solvent, the content of the solvent is appropriately set taking into consideration the desired viscosity of the adhesive 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 total adhesive composition.

[0151] The viscosity of the adhesive composition at 25°C is typically 500 to 20,000 mPa·s, and preferably 1,000 to 5,000 mPa·s, and can be adjusted by changing the types of organic solvents used, their ratios, the concentrations of the film-constituting components, etc., taking into consideration various factors such as the coating method used and the desired film thickness. Here, film-constituting components refer to components contained in the composition other than the solvent.

[0152] The adhesive composition used in the present invention can be produced by mixing the membrane constituent components with a solvent. However, if no solvent is contained, the adhesive composition used in the present invention can be produced by mixing the membrane constituent components.

[0153] In one embodiment, the first step includes a step of applying an adhesive composition to the surface of a semiconductor substrate or a support substrate to form an adhesive coating layer, and a step of joining the semiconductor substrate and the support substrate together via the adhesive coating layer, applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact while performing at least one of a heat treatment and a decompression treatment, 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 applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate into close contact 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, although the adhesive composition is applied to the semiconductor substrate and the release agent composition is applied to the support substrate and heated, the application and heating of the adhesive composition and the release agent composition may be performed sequentially on either substrate. In each of the above embodiments, the treatment conditions to be adopted, such as heat treatment, reduced pressure treatment, or a combination of both, 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 film obtained from both compositions, the film thickness, and the desired adhesive strength.

[0154] Here, for example, the semiconductor substrate is a wafer and the support substrate is a support body, and the adhesive composition may be applied to either or both of the semiconductor substrate and the support substrate.

[0155] Examples of wafers include, but are not limited to, silicon wafers and glass wafers with a diameter of about 300 mm and a thickness of about 770 μm. In particular, the method for cleaning a semiconductor substrate of the present invention can effectively clean a semiconductor substrate having bumps while suppressing damage to the bumps. Specific examples of such semiconductor substrates with bumps include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, which are usually selected appropriately from the following conditions: bump height of about 1 to 200 μm, bump diameter of 1 to 200 μm, and bump pitch of 1 to 500 μm. Specific examples of plated bumps include, but are not limited to, alloy plating mainly containing Sn, such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.

[0156] The support (carrier) is not particularly limited, but may be, for example, a silicon wafer with a diameter of about 300 mm and a thickness of about 700 mm, but is not limited to this.

[0157] Stripping compositions include compositions containing stripping components used in this type of application.

[0158] The coating method is not particularly limited, but is usually a spin coating method. Note that a method of forming a coating film by a separate method such as spin coating and attaching a sheet-like coating film may also be employed, and this method is also referred to as coating or coating film.

[0159] The heating temperature of the applied adhesive composition cannot be generally specified because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is contained, the desired thickness of the adhesive layer, etc., but is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.

[0160] The heating temperature of the applied release agent composition cannot be generally specified because it differs depending on the types and amounts of crosslinking agent, acid generator, acid, etc., whether a solvent is included, 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.

[0161] The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 μm.

[0162] The thickness of the release agent coating layer obtained by applying the release agent composition and heating it is usually 5 to 500 μm.

[0163] The heating temperature is generally determined appropriately within the range of 20 to 150°C, taking into consideration the need to soften the adhesive coating layer to achieve favorable bonding with the release agent coating layer, the need to achieve favorable curing of the release agent coating layer, etc. 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 lower, more preferably 90°C or lower, and from the viewpoint of reliably exhibiting adhesive ability and release ability, the heating time is generally 30 seconds or longer, preferably 1 minute or longer, from the viewpoint of suppressing deterioration of the adhesive layer and other members, but is generally 10 minutes or shorter, preferably 5 minutes or shorter.

[0164] The reduced pressure treatment can be carried out by exposing the semiconductor substrate, adhesive coating layer, and support substrate, or the semiconductor substrate, adhesive coating layer, release agent coating layer, and support substrate, to an atmospheric pressure of 10 to 10,000 Pa. The reduced pressure treatment time is usually 1 to 30 minutes.

[0165] In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together, preferably by a reduced pressure treatment, more preferably by a combination of a heat treatment and a reduced pressure treatment.

[0166] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate, the support substrate, and the layers therebetween and can firmly adhere them to each other, but is usually within the range of 10 to 1000 N.

[0167] The post-heating temperature is preferably 120°C or higher from the viewpoint of obtaining a sufficient curing rate, and preferably 260°C or lower from the viewpoint of preventing deterioration of the substrate, adhesive components, release agent components, etc. The heating time is usually 1 minute or longer from the viewpoint of achieving suitable wafer bonding by curing, and preferably 5 minutes or longer from the viewpoint of stabilizing the physical properties of the adhesive, and is usually 180 minutes or shorter, preferably 120 minutes or shorter, from the viewpoint of avoiding adverse effects on the adhesive layer due to excessive heating. Heating can be carried out using a hot plate, oven, etc. One purpose of the post-heat treatment is to more suitably cure component (A).

[0168] Next, a second step of processing the semiconductor substrate of the stack obtained by the method described above will be described. One example of processing performed on the laminate used in the present invention is processing the back surface of the semiconductor substrate, which is the surface opposite to the circuit surface. Typically, this involves thinning the wafer by polishing the back surface. Using such thinned wafers, through-silicon vias (TSVs) and other processes are formed. The thinned wafers are then peeled off from the support to form a wafer stack, which is then used for three-dimensional packaging. Also, before or after this, electrodes and other processes are formed on the back surface of the wafer. During the wafer thinning and TSV processes, 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 heat-resistant to this 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.

[0169] The third step of separating the processed semiconductor substrate and adhesive layer from the support substrate will now be described. In the third step, the processed semiconductor substrate and adhesive layer are separated from the support substrate. At this time, if a release layer is included in the laminate, the release layer is usually removed together with the support substrate. The method for separating the processed semiconductor substrate and adhesive layer from the semiconductor substrate can be to peel between the adhesive layer and the release layer or support substrate in contact therewith. Examples of such peeling methods include, but are not limited to, laser peeling, mechanical peeling using equipment with sharp edges, and manual peeling.

[0170] Next, a fourth step of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described. In this fourth step, the processed semiconductor substrate having the adhesive layer is cleaned using the method for cleaning a semiconductor substrate of the present invention described above, the detailed conditions being as described above.

[0171] In the method for manufacturing a processed semiconductor substrate of the present invention, the above-mentioned constituent elements and methodological elements relating to the first to fourth steps may be variously changed within the scope of the present invention. [Example]

[0172] 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 apparatus used in the present invention is as follows. (1) Agitator (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 film thickness meter: Tokyo Seimitsu Co., Ltd. Wafer thickness measuring device WT-425 (6) Cleaning device: SUSS MicroTec Auto Cleaning Module (7) Optical microscope: Olympus MX61L Semiconductor / FPD Inspection Microscope

[0173] [1] Preparation of adhesive composition [Preparation Example 1] 95 g of vinyl group-containing MQ resin (manufactured by Wacker Chemie) as (a1), 93.4 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) as a solvent, and 0.41 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) as (A3) were added to a 600 mL stirring vessel dedicated to the planetary centrifugal mixer, and the mixture was stirred for 5 minutes with the planetary centrifugal mixer.

[0174] The resulting mixture was mixed with 19.0 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) having a viscosity of 100 mPa·s as (a2), 29.5 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemical Co.) having a viscosity of 200 mPa·s as (a1), and 1000000 mm 2 65.9 g of polyorganosiloxane (manufactured by Wacker Chemie, trade name AK1000000) of 1 / s and 0.41 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) as (A3) were added, and the mixture was stirred for an additional 5 minutes using a planetary centrifugal mixer.

[0175] Thereafter, 14.9 g of a mixture obtained separately by stirring 0.20 g of a platinum catalyst (manufactured by Wacker Chemie) as (A2) and 17.7 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) as (a1) with a viscosity of 1000 mPa·s for 5 minutes in a planetary centrifugal mixer was added to the resulting mixture, and the mixture was further stirred for 5 minutes in the planetary centrifugal mixer. The resulting mixture was then filtered through a 300-mesh nylon filter to obtain an adhesive composition.

[0176] [2] Preparation of cleaning composition [Preparation Example 2] To 5 g of tetrabutylammonium fluoride trihydrate (Kanto Chemical Co., Ltd.), 47.5 g of N-methyl-2-pyrrolidone dehydrate (Kanto Chemical Co., Ltd.) and 47.5 g of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) were added as solvents and stirred.

[0177] [3] Formation of an adhesive layer on a semiconductor substrate [Manufacturing Example 1] The adhesive composition obtained in Preparation Example 1 was applied to a 300 mm bumped wafer (775 μm thick, SiN substrate, 35 μm bump height, 25 μm bump diameter, Cu pillar + SnAg cap structure) as the device wafer using a spin coater, and heated on a hot plate at 120 ° C for 1.5 minutes and then at 200 ° C for 10 minutes to form a 60 μm thick thin film on the wafer, resulting in a wafer with an adhesive layer. Note that the required number of wafers with adhesive layers were produced.

[0178] [4] Cleaning semiconductor substrates [Example 1] The wafer with the adhesive layer obtained in Production Example 1 was mounted on a dicing ring (manufactured by Disco Corporation) using dicing tape DU-300 (manufactured by Nitto Denko Corporation), and the following procedures were carried out in order, followed by cleaning using a cleaning device. In step E1-1, p-menthane was dropped onto the wafer at 100 mL / min for 10 minutes while the wafer was being rotated at 1500 rpm. In step E1-2, the wafer was dried by spinning at 1000 rpm for 30 seconds. In step E1-3, the wafer was paddle-cleaned for 30 seconds using 200 mL of the cleaning composition obtained in Preparation Example 2. During the paddle cleaning, the wafer was completely immersed in the cleaning composition and was alternately rotated at 20 rpm for 1 second each. In step E1-4, isopropanol was dropped onto the wafer at 200 mL / min for 30 seconds while the wafer was being rotated at 1000 rpm. In step E1-5, the wafer was dried by spinning at 1000 rpm for 30 seconds.

[0179] [Example 2] Washing was carried out in the same manner as in Example 1, except that the following step E2-1 was carried out instead of step E1-1. In step E2-1, paddle cleaning was performed using 300 mL of p-menthane for 5 minutes, and then p-menthane was dropped onto the wafer at 100 mL / min for 5 minutes while the wafer was rotated at 1500 rpm. During paddle cleaning, the wafer was completely immersed in p-menthane and rotated alternately at 40 rpm for 1 second each.

[0180] [Example 3] Washing was carried out in the same manner as in Example 1, except that the following step E3-1 was carried out instead of step E1-1. In step E3-1, paddle cleaning was performed for 10 minutes using 300 mL of p-menthane. During paddle cleaning, the wafer was completely immersed in p-menthane and rotated at 40 rpm alternately for 1 second.

[0181] [Example 4] Washing was carried out in the same manner as in Example 1, except that the following step E4-1 was carried out instead of step E1-1. In step E4-1, the wafer was immersed in 300 mL of p-menthane for 5 minutes, and then p-menthane was added dropwise onto the wafer at 100 mL / min for 5 minutes while rotating the wafer at 1500 rpm. During the immersion, the wafer was completely immersed in p-menthane and was kept stationary without being rotated.

[0182] [Comparative Example 1] The wafer with the adhesive layer was mounted in the same manner as in Example 1, and the following procedures were carried out in order, followed by cleaning using a cleaning device. In step C1-1, p-menthane was dropped onto the wafer at 100 mL / min for 10 minutes while the wafer was being rotated at 1500 rpm. In step C1-2, isopropanol was dropped onto the wafer at 200 mL / min for 30 seconds while the wafer was being rotated at 1000 rpm. In step C1-3, the wafer was dried by spinning at 1000 rpm for 30 seconds. In step C1-4, the wafer was paddle-cleaned for 30 seconds using 200 mL of the cleaning composition obtained in Preparation Example 2. During the paddle cleaning, the wafer was completely immersed in the cleaning composition and was alternately rotated at 20 rpm for 1 second each. In step C1-5, isopropanol was dropped onto the wafer at 200 mL / min for 30 seconds while the wafer was being rotated at 1000 rpm. In step C1-6, the wafer was dried by spinning at 1000 rpm for 30 seconds.

[0183] Comparative Example 2 The wafer with the adhesive layer was mounted in the same manner as in Example 1, and the following procedures were carried out in order, followed by cleaning using a cleaning device. In step C2-1, the wafer was immersed in 100 mL of p-menthane for 5 minutes without being rotated. In step C2-2, the film peeled off by immersion was manually removed while rinsing with p-menthane. In step C2-3, the wafer was immersed in 50 mL of p-menthane for 2 minutes without being rotated. In step C2-4, isopropanol was dripped onto the wafer in a rod shape at 200 mL / min for 30 seconds while the wafer was being rotated at 1000 rpm. In step C2-5, the wafer was dried by spinning at 1000 rpm for 30 seconds.

[0184] Comparative Example 3 The wafer with the adhesive layer was mounted in the same manner as in Example 1, and the following procedures were carried out in order, followed by cleaning using a cleaning device. In step C3-1, the wafer was paddle-cleaned for 1 hour using 200 mL of the cleaning composition obtained in Preparation Example 2. During the paddle cleaning, the wafer was completely immersed in the cleaning composition and was rotated alternately at 20 rpm for 1 second. In step C3-2, isopropanol was dripped onto the wafer in a rod shape at 200 mL / min for 30 seconds while the wafer was being rotated at 1000 rpm. In step C3-3, the wafer was dried by spinning at 1000 rpm for 30 seconds.

[0185] [5] Observation of semiconductor substrates after cleaning The presence or absence of adhesive layer residue and bump damage on the cleaned wafers of the examples and comparative examples was observed using an optical microscope. The results are shown in Table 1.

[0186] [Table 1]

[0187] Residue of the adhesive layer was observed in Comparative Example 1. This is presumably because the adhesive layer, which swelled and peeled off in step C1-1, reattached to the wafer in step C1-2, and was not sufficiently removed during the cleaning time in step C1-4. Adhesive layer residue was also observed in Comparative Example 2. This suggests that adhesive layer residue cannot be completely removed unless a cleaning composition containing salt is used. In Comparative Example 3, no adhesive layer residue was observed, but damage to the bumps was observed, suggesting that prolonged immersion in a cleaning composition containing salt causes bump damage.

[0188] On the other hand, neither adhesive layer residue nor damage to the bumps was observed in any of Examples 1 to 4. This is because the cleaning time using the salt-containing cleaning composition in Step E1-4 was as short as 30 seconds. In Example 1, a step corresponding to step C1-2 in Comparative Example 1 is not included, so that the adhesive layer that has swollen and peeled off does not reattach, and it was confirmed that the adhesive layer residue can be completely removed in step E1-3. In Example 2, it was confirmed that by performing step E2-1 instead of step E1-1, the amount of p-menthane used could be reduced and the adhesive layer residue could be completely removed. In Example 3, by performing step E3-1 instead of step E1-1, it was confirmed that most of the adhesive layer residue could be removed from the wafer in step E1-2, without simultaneously dropping the solvent and rotating the wafer as in step E1-1, and that the adhesive layer residue could be completely removed in the subsequent step E1-3. In Example 4, by performing step E4-1 instead of step E1-1, it was confirmed that most of the adhesive layer residues could be removed from the wafer in step E1-2 by simply immersing it in a solvent, without having to perform paddle cleaning in which the wafer is alternately rotated, and that the adhesive layer residues could be completely removed in the subsequent step E1-3.

Claims

1. 1. A method for cleaning a semiconductor substrate, comprising removing an adhesive layer on a semiconductor substrate, the adhesive layer being formed from a polysiloxane adhesive containing a component (A) that cures by a hydrosilylation reaction, the method comprising: a step (A) of swelling the adhesive layer with an organic solvent (S) containing at least one selected from an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, an ester compound, an ether compound, and a dimethyl silicone compound, and peeling the adhesive layer from the semiconductor substrate; Step (B) of removing the peeled adhesive layer; thereafter, a step (C) of removing adhesive layer residue on the semiconductor substrate using a cleaning agent composition containing a salt, without including a step (N) of rinsing the semiconductor substrate with a solvent (N) containing at least one selected from water and water-soluble solvents; and step (D) of rinsing the semiconductor substrate with a solvent (R) containing at least one selected from water and water-soluble solvents, The cleaning composition containing the salt is a cleaning composition containing an organic solvent containing an amide compound and a quaternary ammonium salt, wherein the amide compound is represented by the following formula (Z): 【Chemistry 1】 In the formula, R 0 represents an ethyl group, a propyl group, or an isopropyl group, and R A and R B each independently represent an alkyl group having 1 to 4 carbon atoms, which may be linear, branched, or cyclic. the adhesive layer is formed from a polysiloxane adhesive containing a component (A) that cures by a hydrosilylation reaction, A method for cleaning a semiconductor substrate, characterized in that the method does not include a step (N) of rinsing the semiconductor substrate with a solvent (N) containing at least one selected from water and water-soluble solvents between the steps (B) and (C).

2. 2. The method for cleaning a semiconductor substrate according to claim 1, wherein the water-soluble solvent contains at least one selected from the group consisting of alcohols, ethers, ketones, nitriles, glycols, alkyl glycols, and dialkyl glycols.

3. 3. The method for cleaning a semiconductor substrate according to claim 2, wherein said alcohol comprises a lower alcohol.

4. 4. The method for cleaning a semiconductor substrate according to claim 3, wherein said lower alcohol comprises one selected from the group consisting of methanol, ethanol, propanol and isopropanol.

5. The method for cleaning a semiconductor substrate according to any one of claims 1 to 4, wherein the step (A) includes a step (A-1) of swelling the adhesive layer on the semiconductor substrate by continuously contacting the adhesive layer with an organic solvent (S) to peel the adhesive layer from the semiconductor substrate.

6. The method for cleaning a semiconductor substrate according to claim 5, wherein the step (A-1) includes a step (A-1-1) of swelling the adhesive layer on the semiconductor substrate by immersing the adhesive layer in an organic solvent (S) to peel off the adhesive layer from the semiconductor substrate.

7. 6. The method for cleaning a semiconductor substrate according to claim 5, wherein the step (A-1) includes a step (A-1-2) of swelling the adhesive layer on the semiconductor substrate by continuously supplying an organic solvent (S) onto the adhesive layer, and peeling the adhesive layer from the semiconductor substrate.

8. The method for cleaning a semiconductor substrate according to any one of claims 1 to 7, wherein the step (B) also serves as a step (K) of drying the semiconductor substrate, or the method includes a step (K) of drying the semiconductor substrate between the step (B) and the step (C).

9. 9. The method for cleaning a semiconductor substrate according to claim 1, wherein in step (B), the peeled adhesive layer is removed by adsorption or suction, or by rotating the semiconductor substrate.

10. 10. The method for cleaning a semiconductor substrate according to claim 9, wherein the water-soluble solvent contains at least one selected from the group consisting of alcohols, ethers, ketones, nitriles, glycols, alkyl glycols, and dialkyl glycols.

11. The method for cleaning a semiconductor substrate according to claim 10, wherein the alcohol comprises a lower alcohol.

12. 12. The method for cleaning a semiconductor substrate according to claim 11, wherein the lower alcohol comprises one selected from the group consisting of methanol, ethanol, propanol, and isopropanol.

13. A method for producing a processed semiconductor substrate, comprising the method for cleaning a semiconductor substrate according to any one of claims 1 to 12.

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