Method for producing disassembly and cleaning composition

Abstract

Provided is a method for producing a decomposing / cleaning composition which improves etching speed retention. A method for producing a decomposing / cleaning composition which contains (A) an N-substituted amide compound in which a hydrogen atom is not directly bonded to a nitrogen atom and (B) a quaternary alkyl ammonium fluoride or a hydrate thereof, said method having a preparation step for mixing the (A) and (B) components in an inert gas atmosphere.

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a decomposition cleaning composition. In particular, the present disclosure relates to a method for producing a composition that can be used to decompose and clean adhesives that remain on a device wafer during a semiconductor wafer thinning process and that contain adhesive polymers used for temporarily bonding the device wafer to a support wafer (carrier wafer). [Background technology]

[0002] In three-dimensional packaging technology for increasing the density of semiconductors, the thickness of each semiconductor wafer is reduced, and multiple semiconductor wafers connected by through-silicon vias (TSVs) are stacked. Specifically, the surface (backside) of a device wafer on which semiconductor devices are formed is polished to make it thinner, and then electrodes including TSVs are formed on the backside.

[0003] In the polishing process of the back surface of the device wafer, a support wafer also called a carrier wafer is temporarily bonded to the semiconductor device forming surface of the device wafer using an adhesive in order to impart mechanical strength to the device wafer. For example, a glass wafer or a silicon wafer is used as the support wafer. After the polishing process, metal wiring or electrode pads containing Al, Cu, Ni, Au, etc., inorganic films such as oxide films and nitride films, or resin layers containing polyimide, etc. are formed on the polished surface (back surface) of the device wafer as necessary. Thereafter, the back surface of the device wafer is bonded to a tape having an acrylic adhesive layer fixed by a ring frame, so that the device wafer is fixed to the tape. Thereafter, the device wafer is separated from the support wafer (debonding), the adhesive on the device wafer is peeled off, and the adhesive residue on the device wafer is washed away using a cleaning agent.

[0004] For the temporary bonding of device wafers, adhesives containing polyorganosiloxane compounds with good heat resistance as adhesive polymers are used. In particular, when the adhesive is a crosslinked polyorganosiloxane compound, the cleaning agent is required to have two functions: cleavage of Si-O bonds and dissolution of decomposition products by a solvent. Examples of such cleaning agents include those in which a fluorine-based compound such as tetrabutylammonium fluoride (TBAF) is dissolved in a polar aprotic solvent. The fluoride ions of TBAF are involved in cleavage of Si-O bonds via the formation of Si-F bonds, and therefore can impart etching performance to the cleaning agent. Polar aprotic solvents can dissolve TBAF and do not form solvations with fluoride ions via hydrogen bonds, and therefore can increase the reactivity of fluoride ions.

[0005] In Non-Patent Document 1 (Advanced Materials, 11, 6, 492 (1999)), a 1.0 M TBAF solution using aprotic THF as a solvent is used to decompose and dissolve and remove polydimethylsiloxane (PDMS).

[0006] In Non-Patent Document 2 (Advanced Materials, 13, 8, 570 (2001)), aprotic solvents such as NMP, DMF and DMSO are used as solvents for TBAF, in addition to THF.

[0007] Non-Patent Document 3 (Macromolecular Chemistry and Physics, 217, 284-291 (2016)) describes the results of investigating the etching rate of PDMS using TBAF / organic solvent for each solvent, and for THF and DMF, which have high etching rates, it also describes a comparison of the etching rates of TBAF solutions using mixed solvents with different THF / DMF ratios. [Prior art documents] [Non-patent literature]

[0008] [Non-Patent Document 1] Advanced Materials, 11, 6, 492 (1999) [Non-Patent Document 2] Advanced Materials, 13, 8, 570 (2001) [Non-Patent Document 3] Macromolecular Chemistry and Physics, 217, 284-291 (2016) Summary of the Invention [Problem to be solved by the invention]

[0009] The role of the solvent in a decomposition cleaning composition containing a fluorine compound such as TBAF and a solvent is thought to be to sufficiently dissolve the highly polar fluorine compound, which is a reactive substance, and to dissolve the decomposition products of the adhesive while ensuring the reactivity of the fluoride ions contained in the fluorine compound.

[0010] The present inventors have found that even when an aprotic N-substituted amide compound is used as a solvent in order to sufficiently dissolve a highly polar fluorine compound and ensure the reactivity of fluoride ions contained in the fluorine compound, the etching rate of the decomposition and cleaning composition may decrease over the storage period after preparation of the decomposition and cleaning composition.

[0011] The present disclosure aims to provide a method for making a decomposition cleaning composition that improves etch rate retention. [Means for solving the problem]

[0012] The present inventors have found that the decrease in etching rate can be suppressed by mixing a quaternary alkylammonium fluoride or a hydrate thereof, and an N-substituted amide compound in which a hydrogen atom is not directly bonded to a nitrogen atom, under an inert gas atmosphere.

[0013] That is, the present invention includes the following [1] to

[14] . [1] A method for producing a decomposition and cleaning composition containing (A) an N-substituted amide compound in which a hydrogen atom is not directly bonded to a nitrogen atom, and (B) a quaternary alkylammonium fluoride or a hydrate thereof, the method comprising a preparation step of mixing (A) and (B) under an inert gas atmosphere. [2] The method for producing the decomposition and cleaning composition according to [1], wherein the decomposition and cleaning composition further contains an ether compound (C), and the method comprises a preparation step of mixing the components (A) to (C) under an inert gas atmosphere. [3] The method for producing a decomposition and cleaning composition according to [1] or [2], wherein the inert gas in the preparation step is nitrogen gas. [4] The method for producing a decomposition and cleaning composition according to any one of [1] to [3], further comprising a sealing step of sealing the prepared decomposition and cleaning composition in a container under an inert gas atmosphere after the preparation step. [5] The method for producing a decomposition and cleaning composition according to [4], wherein the inert gas in the sealing step is nitrogen gas. [6] The (A) N-substituted amide compound has the formula (1): [ka] (In formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms. The method for producing the decomposition and cleaning composition according to any one of [1] to [5], wherein the composition is a 2-pyrrolidone derivative compound represented by the formula: [7] The (A) N-substituted amide compound is represented by the formula (1), 1 The method for producing a decomposition and cleaning composition according to [6], wherein the 2-pyrrolidone derivative compound is a methyl group or an ethyl group. [8] The (C) ether compound is represented by the formula (2): R 2 O(C n H 2n O) x R 3 (2) (In formula (2), R 2 and R 3 each independently represents an alkyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group, n is 2 or 3, and x is an integer from 1 to 4. The method for producing the decomposition and cleaning composition according to [2], which contains a dialkyl ether of a glycol represented by the formula: [9] The method for producing a decomposition cleaning composition according to [8], wherein the dialkyl ether of glycol is dipropylene glycol dimethyl ether.

[10] The (C) ether compound is represented by formula (3): R 4 OR 5 (3) (In the formula, R 4 and R 5 each independently represents an alkyl group having 4 to 8 carbon atoms. The method for producing the decomposition and cleaning composition according to any one of [2], [8] and [9], which contains a dialkyl ether represented by the formula:

[11] The method for producing a decomposition cleaning composition according to

[10] , wherein the dialkyl ether is dibutyl ether.

[12] The (B) quaternary alkyl ammonium fluoride is R 6 R 7 R 8 R 9 N + F - R is a tetraalkylammonium fluoride represented by the formula 6 ~R 9 each independently represents an alkyl group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[13] The method for producing a decomposition cleaning composition according to any one of [1] to

[12] , wherein the decomposition cleaning composition is a decomposition cleaning composition for an adhesive polymer.

[14] The method for producing a decomposition cleaning composition according to

[13] , wherein the adhesive polymer is a polyorganosiloxane compound. Effect of the Invention

[0014] The method for producing the decomposition and cleaning composition of the present disclosure can improve the retention rate of the etching rate, which is advantageous for long-term storage of the decomposition and cleaning composition.

[0015] The above description should not be considered as a disclosure of all embodiments of the present invention and all advantages associated with the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The present invention will be described in further detail below. Note that the present invention is not limited to the following embodiments.

[0017] The decomposition and cleaning composition produced by the production method of the present disclosure contains an N-substituted amide compound (also referred to simply as "N-substituted amide compound" in the present disclosure) as a solvent in which a hydrogen atom is not directly bonded to a nitrogen atom. It is known that N-substituted amide compounds are gradually oxidized to generate oxides when in contact with oxygen. For example, when N-methylpyrrolidone (NMP) is oxidized, NMP derivatives such as N-methylsuccinimide are generated. The oxidation product of this N-substituted amide compound produces a product having a hydrogen atom active against fluoride ions in the decomposition and cleaning composition, which reduces the activity of fluoride ions, and as a result, the etching rate is thought to decrease over time. Therefore, in order to maintain the etching rate, it is considered desirable to suppress the oxidation of the N-substituted amide compound.

[0018] Incidentally, the production process of the decomposition and cleaning composition includes steps such as storing raw materials, putting the raw materials into a mixing tank, adding a solvent, stirring and mixing, filling, and storing. Since these steps are usually performed under an air atmosphere, oxygen dissolves in the solvent, and this dissolved oxygen gradually oxidizes the solvent. Therefore, it is desirable to reduce the dissolution of oxygen into the solvent. From this viewpoint, it is particularly important to sufficiently reduce the oxygen concentration in the gas phase in the stirring and mixing step in which the gas phase and the liquid phase come into contact with each other frequently. In particular, since the quaternary alkyl ammonium fluoride or its hydrate is a solid, it is necessary to perform vigorous stirring to crush and dissolve the quaternary alkyl ammonium fluoride or its hydrate. Therefore, when stirring is performed under an air atmosphere, the dissolution rate of oxygen increases, and even if the subsequent steps are performed under a nitrogen gas atmosphere, the oxidation of the solvent proceeds due to the dissolved oxygen, and the etching rate decreases over time.

[0019] A method for producing a decomposition cleaning composition in one embodiment includes a preparation step of mixing (A) an N-substituted amide compound in which a hydrogen atom is not directly bonded to a nitrogen atom, and (B) a quaternary alkylammonium fluoride or a hydrate thereof under an inert gas atmosphere.

[0020] [Decomposition and cleaning composition] <(A) N-substituted amide compounds in which no hydrogen atom is directly bonded to the nitrogen atom> N-substituted amide compounds in which no hydrogen atom is directly bonded to the nitrogen atom are aprotic solvents with relatively high polarity, and can uniformly dissolve or disperse quaternary alkylammonium fluoride and its hydrate in the composition. In the present disclosure, the "N-substituted amide compound" also includes urea compounds (carbamide compounds) in which no hydrogen atom is directly bonded to the nitrogen atom. As the N-substituted amide compound, various compounds can be used without any particular limitation, for example, non-cyclic N-substituted amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropionamide, N,N-diethylpropionamide, and tetramethylurea, cyclic N-substituted amides such as 2-pyrrolidone derivatives, 2-piperidone derivatives, ε-caprolactam derivatives, 1,3-dimethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (N,N'-dimethylpropyleneurea). Among these, it is preferable to use cyclic N-substituted amides. The N-substituted amide compound may be one type or a combination of two or more types.

[0021] In one embodiment, the N-substituted amide compound has the formula (1): [ka] (In formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms. The 2-pyrrolidone derivative compound represented by formula (1) is represented by the formula (1). Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the 2-pyrrolidone derivative compound represented by formula (1) include N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, and N-butylpyrrolidone.

[0022] N-substituted amide compounds are generally represented by R in formula (1) because of their relatively high polarity, excellent dissolving ability for quaternary alkylammonium fluorides, and ease of availability. 1 is preferably a 2-pyrrolidone derivative compound in which R 1 More preferably, it is a 2-pyrrolidone derivative compound in which is a methyl group, that is, N-methylpyrrolidone.

[0023] In one embodiment, the content of the N-substituted amide compound in the decomposition and cleaning composition is 70 to 99.99% by mass, preferably 80 to 99.95% by mass, and more preferably 90 to 99.9% by mass. When the decomposition and cleaning composition contains an ether compound described later, the total content of the N-substituted amide compound and the ether compound in the decomposition and cleaning composition is preferably 70 to 99.99% by mass, more preferably 80 to 99.95% by mass, and even more preferably 90 to 99.9% by mass.

[0024] <(B) Quaternary alkyl ammonium fluoride or its hydrate> Quaternary alkyl ammonium fluoride or its hydrate releases fluoride ions that are involved in the cleavage of Si-O bonds. The quaternary alkyl ammonium moiety can dissolve the salt of quaternary alkyl ammonium fluoride in an aprotic solvent. As the quaternary alkyl ammonium fluoride, various compounds can be used without particular limitation. Hydrates of quaternary alkyl ammonium fluoride include, for example, trihydrate, tetrahydrate, and pentahydrate. The quaternary alkyl ammonium fluoride may be one type or a combination of two or more types.

[0025] In one embodiment, the quaternary alkyl ammonium fluoride is R 6 R 7 R 8 R 9 N + F - R is a tetraalkylammonium fluoride represented by the formula 6 ~R 9are each independently an alkyl group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Examples of such quaternary alkyl ammonium fluorides include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride. From the standpoints of decomposition and cleaning performance, availability, price, and the like, the quaternary alkyl ammonium fluoride is preferably tetrabutylammonium fluoride (TBAF).

[0026] In one embodiment, the content of the quaternary alkyl ammonium fluoride in the decomposition and cleaning composition is 0.01 to 10 mass %. Here, the "content of the quaternary alkyl ammonium fluoride" refers to the hydrate of the quaternary alkyl ammonium fluoride when the composition contains the hydrate. water The value is calculated as the mass of only the quaternary alkyl ammonium fluoride, excluding the mass of the quaternary alkyl ammonium fluoride. The content of the quaternary alkyl ammonium fluoride in the decomposition and cleaning composition is preferably 0.01 to 5 mass%, more preferably 0.05 to 2 mass%, and even more preferably 0.1 to 1 mass%. In another embodiment, the content of the quaternary alkyl ammonium fluoride in the decomposition and cleaning composition is preferably 0.5 to 9 mass%, more preferably 1 to 8 mass%, and even more preferably 2 to 5 mass%. By making the content of the quaternary alkyl ammonium fluoride 0.01 mass% or more, the adhesive polymer can be effectively decomposed and cleaned, and by making it 10 mass% or less, the corrosion of the metal parts included in the device formation surface of the device wafer can be prevented or suppressed. When it is particularly required to prevent or suppress the corrosion of the metal parts or to reduce the cost associated with the use of the quaternary alkyl ammonium fluoride, the content of the quaternary alkyl ammonium fluoride in the decomposition and cleaning composition may be 4 mass% or less, or 3 mass% or less. When a higher etching rate is required, the content of the quaternary alkyl ammonium fluoride in the decomposition cleaning composition may be 5 mass % or more, 6 mass % or more, or 7 mass % or more.

[0027] <(C) Ether Compounds> The decomposition cleaning composition may contain an ether compound. By combining the ether compound with an N-substituted amide compound, a mixed solvent system showing high affinity to the adhesive surface can be formed. A composition using such a mixed solvent system can achieve a high etching rate by effectively utilizing the reaction activity of the quaternary alkyl ammonium fluoride. As the ether compound, various compounds can be used without particular limitation. The ether compound may be one type or a combination of two or more types. It is preferable that the ether compound does not contain an ester structure or an amide structure.

[0028] In one embodiment, the ether compound has the formula (2): R 2 O(C n H 2n O) x R 3 (2) (In formula (2), R 2 and R 3 each independently represents an alkyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group, n is 2 or 3, and x is an integer from 1 to 4. The dialkyl ethers of glycols represented by the formula:

[0029] Examples of the dialkyl ether of glycol represented by formula (2) include ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol di-n-butyl ether, tetraethylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether, etc. The dialkyl ether of glycol represented by formula (2) is preferably diethylene glycol dimethyl ether or dipropylene glycol dimethyl ether from the viewpoints of decomposition and cleaning performance, availability, price, etc., and more preferably dipropylene glycol dimethyl ether because a high etching rate can be obtained over a wide range of compositions.

[0030] The content of the dialkyl ether of the glycol represented by formula (2) is preferably 10 to 80 mass%, more preferably 15 to 70 mass%, and even more preferably 20 to 60 mass%, when the total of the N-substituted amide compound and the ether compound is taken as 100 mass%. In another embodiment, the content of the dialkyl ether of the glycol represented by formula (2) is preferably 0 to 60 mass%, more preferably 3 to 50 mass%, and even more preferably 5 to 40 mass%, when the total of the N-substituted amide compound and the ether compound is taken as 100 mass%.

[0031] In one embodiment, the ether compound has the formula (3): R 4 OR 5 (3) (In the formula, R 4 and R 5 each independently represents an alkyl group having 4 to 8 carbon atoms. The dialkyl ethers include those represented by the formula:

[0032] The ether compound may contain a dialkyl ether of a glycol represented by formula (2) and a dialkyl ether represented by formula (3). By using two or more types of ether compounds having different polarities in combination, it is possible to effectively increase the affinity for various adhesive surfaces and obtain a composition with a wide range of applications.

[0033] Examples of the dialkyl ether represented by formula (3) include dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, butylhexyl ether, butyloctyl ether, etc. The dialkyl ether represented by formula (3) is preferably dibutyl ether from the viewpoints of decomposition and cleaning performance, availability, price, etc.

[0034] The content of the dialkyl ether represented by formula (3) is preferably 0 to 50 mass%, more preferably 1 to 35 mass%, and even more preferably 2 to 30 mass%, when the total of the N-substituted amide compound and the ether compound is taken as 100 mass%. By setting the content of the dialkyl ether represented by formula (3) to 0 mass% or more and 50 mass% or less, a higher etching rate can be obtained.

[0035] In one embodiment, when the total of the N-substituted amide compound and the ether compound is taken as 100% by mass, the content of the N-substituted amide compound is 10 to 90% by mass, and the content of the ether compound is 90 to 10% by mass. When the total of the N-substituted amide compound and the ether compound is taken as 100% by mass, the content of the N-substituted amide compound is preferably 15 to 85% by mass, the content of the ether compound is preferably 85 to 15% by mass, the content of the N-substituted amide compound is more preferably 25 to 65% by mass, and the content of the ether compound is more preferably 75 to 35% by mass. In another embodiment, when the total of the N-substituted amide compound and the ether compound is taken as 100% by mass, the content of the N-substituted amide compound is preferably 40 to 80% by mass, and the content of the ether compound is preferably 60 to 20% by mass. By setting the content of the N-substituted amide compound and the ether compound in the above range, the quaternary alkyl ammonium fluoride and its hydrate can be uniformly dissolved in the composition, and a high etching rate can be obtained for various adhesive surfaces.

[0036] In one embodiment, when the total of the N-substituted amide compound and the ether compound is taken as 100% by mass, the content of the N-substituted amide compound is 20 to 90% by mass, the content of the dialkyl ether of the glycol represented by formula (2) is 10 to 80% by mass, and the content of the dialkyl ether represented by formula (3) is 0 to 30% by mass. Preferably, the content of the N-substituted amide compound is 25 to 80% by mass, the content of the dialkyl ether of the glycol represented by formula (2) is 20 to 60% by mass, and the content of the dialkyl ether represented by formula (3) is 0 to 30% by mass. In another embodiment, when the total of the N-substituted amide compound and the ether compound is taken as 100% by mass, the content of the N-substituted amide compound is 20 to 90% by mass, the content of the dialkyl ether of the glycol represented by formula (2) is 0 to 70% by mass, and the content of the dialkyl ether represented by formula (3) is 0 to 30% by mass. Preferably, the content of the N-substituted amide compound is 30 to 85 mass%, the content of the dialkyl ether of the glycol represented by formula (2) is 3 to 50 mass%, and the content of the dialkyl ether represented by formula (3) is 0 to 30 mass%.

[0037] <Additives and other ingredients> The decomposition cleaning composition may contain additives such as antioxidants, surfactants, preservatives, and foam inhibitors as optional components, within the scope of not significantly impairing the effects of the present invention.

[0038] In one embodiment, the decomposition cleaning composition is substantially free of or free of protic solvent.For example, the content of protic solvent in the composition can be 5% by weight or less, 3% by weight or less, or 1% by weight or less.The protic solvent that can be included in the composition can be water derived from quaternary alkyl ammonium fluoride hydrate.

[0039] In one embodiment, the decomposition cleaning composition is substantially free or free of aprotic solvents selected from ketones and esters. For example, the content of aprotic solvents selected from ketones and esters in the composition can be 1% by weight or less, 0.5% by weight or less, or 0.1% by weight or less.

[0040] In one embodiment, the decomposition cleaning composition is substantially free of or free of antioxidant.For example, the content of antioxidant in the decomposition cleaning composition can be 1% by mass or less, 0.5% by mass or less, or 0.1% by mass or less.Antioxidants may reduce the activity of fluoride ions.

[0041] [Method of manufacturing the decomposition cleaning composition] The decomposition and cleaning composition is prepared by mixing an N-substituted amide compound, a quaternary alkyl ammonium fluoride or its hydrate, and other optional components under an inert gas atmosphere. For example, in a glove box filled with an inert gas, an N-substituted amide compound, a quaternary alkyl ammonium fluoride or its hydrate, and other optional components are stirred and mixed using a stirrer or the like to dissolve the quaternary alkyl ammonium fluoride or its hydrate in a solvent. The decomposition and cleaning composition prepared in this manner has a low dissolved oxygen content, so that the oxidation of the N-substituted amide compound during storage proceeds slowly, and the decrease in etching rate can be suppressed.

[0042] In order to further suppress the decrease in etching rate, it is preferable to seal the prepared decomposition and cleaning composition in an inert gas atmosphere, that is, to fill and seal the container with an inert gas. This can suppress the dissolution of oxygen into the solvent during storage, and further suppress the oxidation of the N-substituted amide compound. Specifically, a method can be mentioned in which an inert gas is introduced into a container to fill the decomposition and cleaning composition, and after filling, further inert gas is introduced into the gas phase part in the container and sealed. In addition, a method can be mentioned in which a supply nozzle and an exhaust nozzle of the decomposition and cleaning composition are inserted into a sealed container replaced with an inert gas, and the decomposition and cleaning composition is filled into the container while exhausting the inert gas in the container. Furthermore, it is more preferable to perform bubbling with nitrogen gas in order to purge dissolved oxygen.

[0043] The oxygen concentration in the inert gas atmosphere is preferably 0.1 vol % or less, more preferably 0.05 vol % or less, and further preferably 0.01 vol % or less.

[0044] The inert gas is preferably argon gas or nitrogen gas, and more preferably nitrogen gas.

[0045] [Method of use of the disassembly cleaning composition] The composition of the present disclosure can be used as a decomposition cleaning composition for adhesive polymers contained in various adhesives. The adhesive polymer is not particularly limited as long as it can be cleaned using the decomposition cleaning composition of the present disclosure. In addition to the adhesive polymer, the adhesive may contain optional components such as a curing agent, a curing accelerator, a crosslinking agent, a surfactant, a leveling agent, and a filler.

[0046] In one embodiment, the adhesive polymer contains a Si-O bond. The adhesive polymer is depolymerized or loses its crosslinked structure by cleavage of the Si-O bond by the fluoride ion of the quaternary alkyl ammonium fluoride, and becomes soluble in a solvent, so that the adhesive polymer can be removed from the surface of a device wafer or the like.

[0047] The adhesive polymer containing Si-O bonds is preferably a polyorganosiloxane compound. Since the polyorganosiloxane compound contains a large number of siloxane (Si-O-Si) bonds, it can be effectively decomposed and cleaned using the decomposition cleaning composition. Examples of the polyorganosiloxane compound include silicone resins such as silicone elastomers, silicone gels, and MQ resins, as well as modified products thereof such as epoxy modified products, acrylic modified products, methacrylic modified products, amino modified products, and mercapto modified products. The polyorganosiloxane compound may be a silicone modified polymer such as silicone modified polyurethane and silicone modified acrylic resin.

[0048] In one embodiment, the adhesive polymer is an addition-cured silicone elastomer, silicone gel, or silicone resin that includes an ethylenically unsaturated polyorganosiloxane, such as a vinyl-terminated polydimethylsiloxane or a vinyl-terminated MQ resin, and a polyorganohydrogensiloxane, such as a polymethylhydrogensiloxane, as a crosslinker, and is cured with a hydrosilylation catalyst, such as a platinum catalyst.

[0049] In another embodiment, the adhesive polymer comprises an aralkyl-, epoxy-, or phenyl-containing polydiorganosiloxane, particularly an aralkyl-, epoxy-, or phenyl-containing polydimethylsiloxane. An adhesive comprising such an adhesive polymer may be used for temporary adhesion in combination with an adhesive comprising the addition curing silicone. EXAMPLES

[0050] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0051] Preparation of the Decomposition Cleaning Composition Example 1 In a glove box filled with nitrogen gas, 2.281 g of tetrabutylammonium fluoride trihydrate (TBAF·3H2O) (98%) was added to a 125 mL polyethylene container, followed by 34.410 g of N-methylpyrrolidone (NMP) and mixing to dissolve the TBAF·3H2O. In this way, a decomposition and cleaning composition with 5.0 mass% TBAF was prepared. The decomposition and cleaning composition was stored in a polyethylene container filled with nitrogen gas.

[0052] Example 2 In a glove box filled with nitrogen gas, 9.097 g of tetrabutylammonium fluoride trihydrate (TBAF·3H2O) (98%) was added to a 125 mL polyethylene container, and 67.467 g of N-methylpyrrolidone (NMP), 6.687 g of dipropylene glycol dimethyl ether (hereinafter referred to as "DPGDME"), and 12.666 g of dibutyl ether (DBE) were added in that order and mixed to dissolve TBAF·3H2O. In this way, a decomposition and cleaning composition of 7.7 mass% TBAF mixed solvent with a mass ratio of NMP: dipropylene glycol dimethyl ether: dibutyl ether of 0.777: 0.077: 0.146 was prepared. The decomposition and cleaning composition was stored in a polyethylene container filled with nitrogen gas.

[0053] Example 3 A decomposition cleaning composition was prepared in the same manner as in Example 2, except that the composition was as shown in Table 3.

[0054] Comparative Examples 1 to 3 The decomposition and cleaning compositions were prepared in the same manner as in Examples 1 and 2, except that the compositions were as shown in Tables 1 to 3 and were weighed and mixed in the air. The prepared decomposition and cleaning compositions were stored in sealed polyethylene containers in the air.

[0055] Preparation of silicon wafer specimens having an adhesive layer containing a polyorganosiloxane compound An addition-curing silicone resin was applied by spin coating onto a 12-inch (300 mm) silicon wafer (thickness 770 μm) so that the dry film thickness was 110 μm. The silicon wafer was then heated on a hot plate at 140° C. for 15 minutes and at 190° C. for 10 minutes to form an adhesive layer on the silicon wafer. The silicon wafer with the adhesive layer was divided into test pieces measuring 4 cm x 4 cm, and the thickness of the center of the test piece was measured using a micrometer.

[0056] Cleaning Test 7.0 mL of the decomposition cleaning composition immediately after preparation (within 30 minutes after preparation) was taken out of the mixing tank and put into a SUS petri dish with a diameter of 90 mm. One test piece was immersed in the decomposition cleaning composition, and the petri dish was shaken back and forth at a frequency of 1 Hz for 5 minutes at room temperature (25 ° C). After immersion, the test piece was removed with tweezers, immersed in isopropyl alcohol (IPA), and further rinsed thoroughly using a washing bottle of IPA. Thereafter, the test piece was immersed in ion-exchanged water (DIW), and similarly rinsed thoroughly using a washing bottle of DIW. Nitrogen gas was sprayed onto the test piece to dry the adhering water, and then the test piece was heated and dried for 30 minutes in a dryer at 125 ° C. The thickness of the center of the test piece after drying was measured using a micrometer.

[0057] The etching rate (ER) of the decomposition cleaning composition was calculated by dividing the difference in thickness of the test piece before and after immersion by the immersion time (5 minutes) in the decomposition cleaning composition. Etching rate (ER) (μm / min) = [(thickness of test piece before immersion - thickness of test piece after immersion, washing and drying) (μm)] / immersion time (min)

[0058] After preparation, the decomposition and cleaning compositions were stored at room temperature in a nitrogen gas atmosphere or in the air for a certain number of days, and cleaning tests were carried out in the same manner, and the etching rates were calculated. The results are shown in Tables 1 to 3. In Tables 1 to 3, the retention rate indicates the retention rate of the etching rate when the retention rate immediately after preparation in a nitrogen gas atmosphere (within 30 minutes after preparation) is taken as 1.00.

[0059] [Table 1] [Table 2] [Table 3]

[0060] The decomposition and cleaning compositions of Examples 1 to 3 exhibited higher retention rates of the etching rate than the decomposition and cleaning compositions of Comparative Examples 1 to 3. [Industrial Applicability]

[0061] The method for producing the decomposition and cleaning composition of the present disclosure can be used for producing and storing a composition for decomposing and cleaning residues of adhesives used in the thinning process of semiconductor wafers, particularly adhesives containing a polyorganosiloxane compound as an adhesive polymer, from device wafers.

Claims

1. A method for producing a decomposition cleaning composition containing (A) an N-substituted amide compound in which a hydrogen atom is not directly bonded to a nitrogen atom, and (B) a quaternary alkyl ammonium fluoride or a hydrate thereof, the method comprising a preparation step of mixing (A) and (B) under an inert gas atmosphere, and a sealing step of sealing the prepared decomposition cleaning composition in a container under an inert gas atmosphere after the preparation step.

2. The method for producing the decomposition and cleaning composition according to claim 1, further comprising a preparation step of mixing the components (A) to (C) under an inert gas atmosphere, wherein the decomposition and cleaning composition further contains an ether compound (C).

3. The method for producing a decomposition and cleaning composition according to claim 1 or 2, wherein the inert gas in the preparation step is nitrogen gas.

4. The method for producing a decomposition cleaning composition according to any one of claims 1 to 3, wherein the inert gas in the sealing step is nitrogen gas.

5. The (A) N-substituted amide compound is represented by the formula (1): 【Chemistry 1】 (In formula (1), R １ represents an alkyl group having 1 to 4 carbon atoms. The method for producing the decomposition cleaning composition according to any one of claims 1 to 4, wherein the 2-pyrrolidone derivative compound is represented by the following formula:

6. The (A) N-substituted amide compound is represented by the formula (1) R １ The method for producing a decomposition cleaning composition according to claim 5, wherein the compound is a 2-pyrrolidone derivative compound in which R is a methyl group or an ethyl group.

7. The (C) ether compound is represented by the formula (2): R ２ O(C ｎ H ２ｎ O) ｘ R ３ (2) (In formula (2), R ２ and R ３ each independently represents an alkyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group, n is 2 or 3, and x is an integer from 1 to 4. The method for producing the decomposition cleaning composition according to claim 2, which contains a dialkyl ether of a glycol represented by the formula:

8. The method for producing a decomposition cleaning composition according to claim 7, wherein the dialkyl ether of glycol is dipropylene glycol dimethyl ether.

9. The (C) ether compound is represented by the formula (3): R ４ OR ５ (3) (In the formula, R ４ and R ５ each independently represents an alkyl group having 4 to 8 carbon atoms. The method for producing the decomposition cleaning composition according to claim 2, 7 or 8, which contains a dialkyl ether represented by the formula:

10. The method for producing a decomposition cleaning composition according to claim 9, wherein the dialkyl ether is dibutyl ether.

11. The (B) quaternary alkyl ammonium fluoride is R ６ R ７ R ８ R ９ N ＋ F － R is a tetraalkylammonium fluoride represented by the formula: ６ ~R ９ The method for producing a decomposition cleaning composition according to any one of claims 1 to 10, wherein each of the alkyl groups is independently selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

12. The method for producing a disassembly cleaning composition according to any one of claims 1 to 11, wherein the disassembly cleaning composition is a disassembly cleaning composition for an adhesive polymer.

13. The method for producing a decomposition cleaning composition according to claim 12, wherein the adhesive polymer is a polyorganosiloxane compound.

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