Cleaning solution composition

Abstract

To provide a cleaning solution composition having improved cleaning power. [Solution] The cleaning solution composition according to an embodiment of the present invention comprises a cyclic amide compound, a polar aprotic solvent, and a fluorine compound. The cleaning solution composition rapidly removes silicone polymers without leaving any residue, while not etching metal films or the like. The cleaning solution composition can be used for cleaning wafers in semiconductor manufacturing processes.

Description

Technical Field

[0001] The present disclosure relates to a cleaning liquid composition.

Background Art

[0002] In the manufacturing process of semiconductor elements, after forming an electronic circuit or the like on the surface of a semiconductor wafer, the thickness of the wafer can be reduced by performing back grinding (for example, back grinding) on the back surface of the wafer. In this case, a support can be attached to the back surface of the wafer using a silicone-based resin in order to protect the back surface of the wafer and fix the wafer. The support can reinforce the wafer with reduced thickness, and a back electrode or the like can also be formed on the grinding surface of the wafer.

[0003] After performing processes such as back grinding of the wafer and formation of a back electrode, the support is removed from the back surface of the wafer, the attached silicone-based resin is peeled off, and the wafer is cut to manufacture chips.

[0004] Recently, a chip stacking technology using through electrodes (for example, silicon through electrodes) penetrating a wafer has been developed. In this case, the electronic circuits of a plurality of chips can be electrically connected using the through electrodes. Thereby, the high integration degree and operating speed of the chips can be improved.

[0005] In order to reduce the thickness of an aggregate in which a plurality of chips are stacked, after performing back grinding of the wafer, the support and the silicone-based resin can be bonded to the wafer as described above.

[0006] Thermal curing can be performed to increase the adhesion force between the wafer and the support. When peeling the silicone-based resin, the silicone-based resin attached to the cured electronic components may remain on the support and the back surface of the wafer.

[0007] Various cleaning compositions have been proposed as methods for removing silicone-based adhesives, but these can sometimes cause corrosion of metal wiring or reduce the rate at which the silicone adhesive is removed. [Overview of the project] [Problems that the invention aims to solve]

[0008] One objective of this disclosure is to provide a cleaning solution composition having improved cleaning power. [Means for solving the problem]

[0009] 1. A cleaning solution composition comprising a cyclic amide compound represented by the following chemical formula 1, a polar aprotic solvent, and a fluorine compound. [ka] (In the above chemical formula 1, R1 is hydrogen, a C1-C5 alkyl group, or a C2-C5 alkenyl group, and either R2 or R3 is a C1-C15 alkylene group, a C2-C15 alkenylene group, a C3-C20 cycloalkylene group, a C3-C20 cycloalkenylene group, or a C6-C20 arylene group) Either R2 or R3 is a direct bond, an alkylene group C1-C15, an alkenylene group C2-C15, a cycloalkylene group C3-C20, a cycloalkenylene group C3-C20, a heteroarylene group C3-C10, a heterocycloalkylene group C3-C10, or an arylene group C6-C20, and m is either 0 or 1.

[0010] 2. A cleaning solution composition in which, in item 1 above, R2 in chemical formula 1 is a C3-C7 alkylene group or a C6-C9 arylene group.

[0011] 3. A cleaning solution composition in which, in item 1 above, R1 in chemical formula 1 is hydrogen, a methyl group, or a vinyl group.

[0012] 4. In any of the above items 1 to 3, the cyclic amide compound comprises at least one selected from the group consisting of γ-valerolactam, ε-caprolactam, N-methyl-ε-caprolactam, N-vinyl-ε-caprolactam, ω-heptalactam, ω-octaractam, glycyl-L-proline lactam, isatin, and vinlactam, in a cleaning solution composition.

[0013] 5. In any of the above items 1 to 3, the content of the cyclic amide compound is 0.001% to 10% by weight relative to the total weight of the cleaning solution composition.

[0014] 6. In any of the above items 1 to 3, the polar aprotic solvent comprises at least one selected from the group consisting of linear amide solvents, amine solvents, ketone solvents, morpholine solvents, pyrrolidine solvents, pyrrolidone solvents, urea solvents, lactone solvents, sulfoxide solvents, phosphate solvents, oxazolidone solvents, piperazine solvents, and alkylene glycol alkyl ether solvents, a cleaning solution composition.

[0015] 7. In any of the above items 1 to 3, the content of the polar aprotic solvent is 88% to 99% by weight relative to the total weight of the cleaning solution composition.

[0016] 8. In any of the above items 1 to 3, the fluorine-based compound comprises an ionic bond between a nitrogen-based cation, a phosphorus-based cation, or a sulfur-based cation and a fluorine anion, wherein the cleaning solution composition is characterized by this bond.

[0017] 9. In item 8 above, the cleaning solution composition comprises an ammonium cation to which three or more C1-C10 alkyl groups are bonded.

[0018] 10. A cleaning solution composition in which, in any of the above items 1 to 3, the fluorine-based compound is in hydrate form.

[0019] 11. In any one of Items 1 to 3 above, the fluorine-based compound is at least one selected from the group consisting of tetrabutylammonium bifluoride (TBAF·HF), tetrabutylammonium fluoride (TBAF), tetraoctylammonium fluoride (TOAF), benzyltrimethylammonium fluoride (BTMAF), tetra-n-butylammonium fluoride hydrate, tetra-n-butylammonium fluoride trihydrate, benzyltrimethylammonium fluoride hydrate, tributylsulfonium fluoride, and tetrabutylphosphonium fluoride, and the cleaning liquid composition.

[0020] 12. In any one of Items 1 to 3 above, the content of the fluorine-based compound is 1% by weight to 12% by weight based on the total weight of the cleaning liquid composition, and the cleaning liquid composition.

[0021] 13. In any one of Items 1 to 3 above, the cleaning liquid composition does not contain an ammonium hydroxide-based compound, a metal hydroxide, an alcohol-based compound, a carboxylic acid-based compound, a peroxide compound, or an inorganic acid compound.

Advantages of the Invention

[0022] The cleaning liquid composition according to an exemplary embodiment of the present invention can efficiently remove silicone-based resins such as linear and network-shaped ones. Further, the cleaning liquid composition can selectively remove the silicone-based resin without etching or corroding the metal member.

[0023] The cleaning liquid composition can decompose and dissolve the silicone-based resin into units of silicone-based oligomers and remove them. Thereby, the silicone-based resin can be removed more quickly, and a high-quality semiconductor element can be provided. [[ID=​​​​​​

[0025] The embodiments of this disclosure are described in detail below. However, these embodiments are illustrative and do not limit the scope of this disclosure.

[0026] As used herein, the term "Ca~Cb Y group" refers to a Y group having a number of carbon atoms a~b. For example, Ca~Cb refers to the number of carbon atoms of an unsubstituted Y group, and additional substituents may be attached to the Y group.

[0027] In the semiconductor manufacturing process, components may be moved, surface treated, and subjected to processes such as attachment of other components while temporarily attached. The attachment is performed using a silicone-based adhesive, and after the processes performed while the components are attached, the components can be separated from each other. After the separation of the components, the silicone-based adhesive may remain on the surface of the individual components, but the silicone-based adhesive can be cleaned and removed using a cleaning composition according to an embodiment of the present invention.

[0028] The cleaning solution composition contains a fluorine-based compound. The fluorine-based compound can react with silicone atoms and can cleave the chains of silicone polymers, thereby decomposing the silicone polymers into silicone oligomers.

[0029] According to exemplary embodiments, the fluorinated compound may be in hydrate form. For example, the fluorinated compound may be a hydrate in which five or fewer water molecules are bonded to each molecule. The hydrate form of the fluorinated compound may contain nitrogen cations as described later.

[0030] The fluorinated compound may contain ionic bonds between nitrogen cations, phosphorus cations, or sulfur cations, and fluorine anions. For example, the fluorinated compound may contain ionic bonds between ammonium cations, phosphonium cations, or sulfonium cations, and fluorine anions.

[0031] According to exemplary embodiments, the nitrogen-based cation may include an ammonium-based cation to which three or more C1-C10 alkyl groups are bonded. For example, the nitrogen-based cation may include four C1-C10 alkyl groups, or three C1-C10 alkyl groups and a C6-C20 aromatic group. The aromatic group may include, for example, a phenyl group or a benzyl group.

[0032] The phosphorus cation may include a phosphonium cation. The phosphonium cation may include four organic groups bonded to the phosphorus atom. The organic groups may include C1-C22 aliphatic hydrocarbon groups or C6-C20 aromatic groups. For example, the phosphorus cation may be a tetrabutylphosphonium cation.

[0033] The sulfur-based cation may include a sulfonium-based cation. The sulfonium-based cation may include three organic groups bonded to the sulfur atom. The organic groups may include C1-C22 aliphatic hydrocarbon groups or C6-C20 aromatic groups. For example, the sulfur-based cation may be a tetrabutylsulfonium cation.

[0034] According to exemplary embodiments, the fluorinated compound may include tetrabutylammonium bifluoride, tetrabutylammonium fluoride (TBAF), tetraoctylammonium fluoride (TOAF), benzyltrimethylammonium fluoride (BTMAF), tetra-n-butylammonium fluoride hydrate, tetra-n-butylammonium fluoride trihydrate, benzyltrimethylammonium fluoride hydrate, tributylsulfonium fluoride, tetrabutylphosphonium fluoride, and the like. These may be used individually or in combination of two or more.

[0035] According to exemplary embodiments, the content of the fluorinated compound may be 0.1% to 20% by weight of the total weight of the composition. According to some embodiments, the content of the fluorinated compound may be 3% to 10% by weight of the total weight of the composition.

[0036] Within the aforementioned range, silicone-based adhesives can be removed quickly and effectively without corroding the metal film.

[0037] The cleaning solution composition according to an exemplary embodiment includes a cyclic amide compound. The cyclic amide compound can prevent corrosion of the exposed metal film without inhibiting the silicone polymer removal reaction of the fluorine compound.

[0038] The aforementioned cyclic amide compound is represented by the following chemical formula 1.

[0039] [ka]

[0040] In chemical formula 1, R1 is hydrogen, a C1-C5 alkyl group, or a C2-C5 alkenyl group. According to some embodiments, R1 may be hydrogen, a C1-C3 alkyl group, or a C2-C4 alkenyl group. For example, R1 may be hydrogen, a methyl group, or a vinyl group.

[0041] In chemical formula 1, either R2 or R3 is a C1-C15 alkylene group, a C2-C15 alkenylene group, a C3-C20 cycloalkylene group, a C3-C20 cycloalkenylene group, or a C6-C20 arylene group.

[0042] Either R2 or R3 is a direct bond, an alkylene group C1-C15, an alkenylene group C2-C15, a cycloalkylene group C3-C20, a cycloalkenylene group C3-C20, a heteroarylene group C3-C10, a heterocycloalkylene group C3-C10, or an arylene group C6-C20.

[0043] In some embodiments, R2 may be an alkylene group of C1-C15, an alkenylene group of C2-C15, a cycloalkylene group of C3-C20, a cycloalkenylene group of C3-C20, or an arylene group of C6-C20. R3 may be a direct bond, an alkylene group of C1-C15, an alkenylene group of C2-C15, a cycloalkylene group of C3-C20, a cycloalkenylene group of C3-C20, a heteroarylene group of C3-C10, a heterocycloalkylene group of C3-C10, or an arylene group of C6-C20.

[0044] In some embodiments, R2 may be an alkylene group C1-C8, an alkenylene group C2-C8, a cycloalkenylene group C4-C7, a heterocycloalkylene group C3-C6, or an arylene group C6-C12. R3 may be directly bonded.

[0045] In some embodiments, R3 may be an alkylene group C1-C8, an alkenylene group C2-C8, a cycloalkenylene group C4-C7, a heterocycloalkylene group C3-C6, or an arylene group C6-C12. R2 may be directly bonded.

[0046] The alkylene group is a divalent linear or branched saturated hydrocarbon group, and may include, for example, a methylene group, an ethylene group, or a propylene group.

[0047] The aforementioned alkenylene group is a divalent linear or branched unsaturated hydrocarbon group containing a carbon-carbon double bond, and may include, for example, an ethenylene group or a propenylene group.

[0048] The cycloalkenylene group is a divalent cyclic unsaturated hydrocarbon group containing a carbon-carbon double bond, and may include, for example, a cyclopentenylene group or a cyclohexenylene group.

[0049] The heterocycloalkylene group may be a divalent cyclic saturated organic group containing at least one heteroatom such as nitrogen, oxygen, sulfur, or phosphorus. For example, the heterocycloalkylene group may be a divalent cyclic saturated organic group obtained by removing any two hydrogen atoms from a heterocycle such as pyrrolidine, piperidine, aziridine, azetidine, oxolane, oxane, oxetane, thiolane, or thian.

[0050] The aforementioned arylene group is a divalent cyclic hydrocarbon group containing an aromatic ring, and may include, for example, a phenylene group.

[0051] According to an exemplary embodiment, in the chemical formula 1, R2 may be a C3-C7 alkylene group or a C6-C9 arylene group. For example, R2 may be a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, or a phenylene group.

[0052] In the above chemical formula 1, m is either 0 or 1.

[0053] According to exemplary embodiments, the cyclic amide compound may include at least one selected from the group consisting of γ-valerolactam, ε-caprolactam, N-methyl-ε-caprolactam, N-vinyl-ε-caprolactam, ω-heptalactam, ω-octalactam, glycyl-L-proline lactam, isatin, and vinlactam.

[0054] According to exemplary embodiments, the content of the cyclic amide compound may be 0.001% to 10% by weight of the total weight of the composition. According to some embodiments, the content of the cyclic amide compound may be 0.001% to 5% by weight, 0.001% to 1% by weight, or 0.005% to 1% by weight of the total weight of the composition.

[0055] Within the aforementioned range, corrosion of the metal film can be suppressed without inhibiting the reaction between the fluorine-based compound and the silicone-based polymer.

[0056] The cleaning composition contains a polar aprotic solvent. The polar aprotic solvent can penetrate between the silicone polymer chains to be removed, causing the silicone polymer to swell. It can also dissolve the fluorine compound and the decomposed silicone oligomer.

[0057] The aforementioned polar aprotic solvent promotes the dissociation and segregation of cations and anions of the fluorinated compound, thereby increasing the concentration of fluorinated ions that can participate in the reaction with the silicone polymer. This improves the cleaning performance of the composition with respect to silicone resins.

[0058] According to exemplary embodiments, the polar aprotic solvent may include at least one selected from the group consisting of linear amide solvents, amine solvents, ketone solvents, morpholine solvents, pyrrolidine solvents, pyrrolidone solvents, urea solvents, lactone solvents, sulfoxide solvents, phosphate solvents, oxazolidone solvents, piperazine solvents, and alkylene glycol alkyl ether solvents.

[0059] Non-limiting examples of the linear amide solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N-ethyl-N-methylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutylamide, N,N-dimethylisobutylamide, N,N-dimethylpentanamide, N,N-dimethylpropanamide, N,N-diethylpropanamide, N,N-dibutylpropanamide, and the like.

[0060] The amine-based solvent may include primary to tertiary aliphatic amines, alicyclic amines, heterocyclic amines, aromatic amines, and the like.

[0061] Non-limiting examples of the aforementioned ketone solvents include 2-butanone, dicyclopropyl ketone, cyclopropyl methyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 3-pentanone, 2-pentanone, 3-methyl-2-pentanone, acetylacetone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 3-hexanone, 2-hexanone, dicycloketone, 1-cyclopentyl ethanoone, 3-methyl-2-hexanone, and 2-methyl-3-hexanone. This may include isoamyl ketones, amyl ketones, 4-heptanone, 3-heptanone, 2-heptanone, 5-nonanone, 2,4-dimethyl-3-pentanone, ethyl-isobutyl ketone, 3,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 3-octanone, 5-methyl-2-hexanone, 5-methyl-3-heptanone, 3-methyl-4-heptanone, 2,5-dimethyl-3-hexanone, 2,6-dimethyl-4-hexanone, 2,6-dimethyl-4-heptanone, etc.

[0062] The pyridine solvent may include the compound represented by the following chemical formula 2:

[0063] [ka]

[0064] In chemical formula 2, R4 may be hydrogen, a C1-C10 linear aliphatic hydrocarbon group or a C3-C10 branched aliphatic hydrocarbon group, a halogen (e.g., F, Cl, Br, or I), an aldehyde group (-CHO), an acetaldehyde group (-COCH3), a C1-C4 alkoxy group, a vinyl group, an acetylene group, a cyano group (-CN), or a methyl sulfide group (-SCH3).

[0065] Non-limiting examples of the pyridine-based solvent include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-isopropylpyridine, 4-amylpyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5-lutidine, or 2,4,6-trimethylpyridine.

[0066] The morpholine-based solvent can be represented by the following chemical formula 3.

[0067] [ka]

[0068] In chemical formula 3, R5 is hydrogen; a C1-C6 linear aliphatic hydrocarbon group or a C3-C6 branched aliphatic hydrocarbon group; a vinyl group; a cyano group (-CN); a C1-C4 aliphatic hydrocarbon group substituted with a tertiary amine; a C1-C4 alkyl group, a cyano group (-CN), a halogen group (e.g., F, Cl, Br, I), or an aldehyde group (-CHO) substituted with a phenyl or pyridine group. X is oxygen or -NR6-. R6 is a C1-C4 aliphatic hydrocarbon group.

[0069] Non-limiting examples of the morpholine-based solvent include N-methylmorpholine, N-ethylmorpholine, N-allylmorpholine, N-butylmorpholine, and N-isobutylmorpholine.

[0070] Non-limiting examples of the pyrrolidone solvents mentioned above may include N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-vinylpyrrolidone (NVP), and the like.

[0071] The urea-based solvent may include the compound represented by the following chemical formula 4.

[0072] [ka]

[0073] In chemical formula 4, X is oxygen or -NR8-, and R8 is a C1-C6 linear aliphatic hydrocarbon group; a C3-C6 branched or cyclic aliphatic hydrocarbon group; or a C1-C4 aliphatic hydrocarbon group substituted with a vinyl group, phenyl group, acetylene group, methoxy group, or dimethylamino group.

[0074] Non-limiting examples of the urea-based solvents mentioned above may include tetramethylurea, tetraethylurea, tetrabutylurea, and the like.

[0075] The phosphate solvent may include the compound represented by the following chemical formula 5.

[0076] [ka]

[0077] In chemical formula 5, R9~R 11 Each of these is independently a C1-C8 linear aliphatic hydrocarbon group or a C3-C8 branched aliphatic hydrocarbon group; a C3-C8 divalent aliphatic hydrocarbon group that forms a ring with adjacent oxygen atoms; an unsubstituted or C1-C4 substituted phenyl group; a C2-C4 substituted with a halogen (e.g., F, Cl, Br, I); or a halogen-substituted phenyl group.

[0078] Non-limiting examples of the phosphate solvents mentioned above may include triethyl phosphate, tributyl phosphate, triamyl phosphate, and triallyl phosphate.

[0079] Non-limiting examples of the lactone-based solvents include beta-butyrolactone, gamma-macarolactone, gamma-heptanolactone, gamma-octanolactone, gamma-nonalactone, gamma-decanolactone, delta-caprolactone, delta-heptanolactone, delta-octanolactone, delta-nonalactone, delta-decanolactone, delta-dodecanolactone, and the like.

[0080] Non-limiting examples of the sulfoxide solvent include dimethyl sulfoxide (DMSO), dibutyl sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide, and methylphenyl sulfoxide.

[0081] Non-limiting examples of the oxazolidone solvents mentioned above may include 2-oxazolidone, 3-methyl-2-oxazolidone, and the like.

[0082] Non-limiting examples of the piperazine-based solvents mentioned above may include dimethylpiperazine, dibutylpiperazine, and the like.

[0083] The alkylene glycol alkyl ether solvent can be represented by the following chemical formula 6.

[0084] [ka]

[0085] In chemical formula 6, R 12 and R 13 Each of the following is independently a C1-C4 alkyl group, Ra and Rb are independently a hydrogen or methyl group, and p is an integer from 2 to 4.

[0086] Non-limiting examples of the alkylene glycol alkyl ether solvent include diethylene glycol diethyl ether (diglyme), diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether (triglyme), tetraethylene dimethyl ether (tetraglyme), dipropylene glycol dimethyl ether, and the like.

[0087] The aforementioned polar aprotic solvent can be any of the compounds described above, either individually or in combination of two or more. For example, the polar aprotic solvent may include an amide solvent and an alkylene glycol alkyl ether solvent, an amide solvent and a ketone solvent, a sulfoxide solvent and a ketone solvent, or an amide solvent and a ketone solvent.

[0088] According to exemplary embodiments, the polar aprotic solvent may be included in the cleaning solution composition as a residue other than the solids. The residue may mean the content in the total weight of the composition, excluding the cyclic amide compound and the fluorine compound, which may be solutes. The residue may refer to a variable content that can be adjusted by adding additional other components.

[0089] According to exemplary embodiments, the content of the polar aprotic solvent may be 88% to 99% by weight of the total weight of the composition. According to some embodiments, the content of the polar aprotic solvent may be 89% to 97% by weight of the total weight of the composition.

[0090] According to some embodiments, the cleaning solution composition may further contain water. In one embodiment, water may be included in the cleaning solution composition in the form of a hydrate with the fluorine compound. In one embodiment, water may be added separately to the cleaning solution composition.

[0091] The water content in the total weight of the cleaning solution composition may be 4% by weight or less. According to some embodiments, the water content in the total weight of the cleaning solution composition may be 3% by weight or less, or 2% by weight or less. Within this range of content, corrosion of the metal film can be prevented.

[0092] According to exemplary embodiments, the cleaning solution composition does not necessarily contain ammonium hydroxide compounds, metal hydroxides, alcohol compounds, carboxylic acid compounds, peroxide compounds, or inorganic acid compounds.

[0093] For example, the ammonium hydroxide-based compound may include ammonium hydroxide, trimethylammonium hydroxide, triethylammonium hydroxide, and the like.

[0094] For example, the metal hydroxide may include NaOH, KOH, Ca(OH)2, Al(OH)3, and the like.

[0095] For example, the alcohol-based compound may include methanol, ethanol, isopropyl alcohol (IPA), methoxypropanol, and the like.

[0096] For example, the carboxylic acid compound may be an organic acid. The organic acid may include formic acid, acetic acid, propionic acid, butyric acid, palmitic acid, stearic acid, oleic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, glutaric acid, adipic acid, sulfosuccinic acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, lactic acid, malic acid, citric acid, tartaric acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, naphthoic acid, nicotinic acid, toluic acid, anisic acid, cumic acid, phthalic acid, and the like.

[0097] For example, the peroxide compound may include hydrogen peroxide, benzoyl peroxide, ammonium persulfate, and the like.

[0098] For example, the inorganic acid compound may include hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, nitric acid, bromate, iodic acid, and the like.

[0099] In some embodiments, the cleaning solution composition may be substantially composed of the cyclic amide compound, the polar aprotic solvent, and the fluorinated compound. For example, the cleaning solution composition may not contain any other components other than the cyclic amide compound, the polar aprotic solvent, and the fluorinated compound. For example, the total content of the cyclic amide compound, the polar aprotic solvent, and the fluorinated compound in the cleaning solution composition may be 100% by weight.

[0100] The cleaning solution composition can dissolve silicone polymers. For example, the silicone polymer may include a linear silicone polymer or a network silicone polymer in which the linear silicone polymer is crosslinked.

[0101] The silicone polymer may be the main component of the silicone adhesive described above. For example, the silicone polymer may include polydimethylsiloxane polymers, polyorganosiloxane polymers, and the like.

[0102] The cleaning solution composition can remove the film containing the silicone polymer at a rate of 10 μm / min or more. For example, when a wafer on which a film containing the silicone polymer has been formed is immersed in the cleaning solution composition, the reduction in the thickness of the film per minute may be 10 μm or more.

[0103] Within the aforementioned range, silicone-based polymers can be removed more quickly, improving the productivity of semiconductor devices.

[0104] According to exemplary embodiments, the cleaning solution composition can have a low etching rate on metal members. The metal members may include or be made of metal, such as metal wiring or bump balls of a semiconductor device.

[0105] For example, non-limiting examples of the metal component include Sn-containing alloys such as Sn, Sn-Ag alloys, Sn-Au alloys, and Sn-Ag-Cu alloys; double or triple film structures such as Sn / Cu, Sn / Ni, Sn / Ni / Cu, Sn-Ag / Cu, Sn-Ag / Ni, Sn-Ag / Ni / Cu, Sn-Au / Cu, Sn-Au / Ni, Sn-Au / Ni / Cu, Sn-Ag-Cu / Ni, Sn-Ag-Cu / Ni / Cu, and Sn-Ag-Cu / Cu; and metal films composed of Cu.

[0106] For example, the metal component will not be damaged or discolored even when exposed to the cleaning solution composition. As a result, the cleaning solution composition can be used in the manufacturing process of semiconductor elements applied to optical devices.

[0107] For example, the cleaning solution composition does not alter the surface morphology of the metal component. This makes it possible to provide high-quality semiconductor devices.

[0108] The cleaning solution composition can be used in various semiconductor manufacturing processes. As mentioned above, the cleaning solution composition can be used in the cleaning process of silicone adhesives, but the applications of the cleaning solution composition are not limited to this. For example, the cleaning solution composition can also be used in the cleaning process of acrylic adhesives or for cleaning residues remaining after removing adhesive tape.

[0109] The embodiments of the present invention will be further described below with reference to specific experimental examples. However, these embodiments are merely illustrative of the present invention and do not limit the scope of the attached claims. It will be obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope of the present invention and the technical concept, and that such variations and modifications naturally fall within the scope of the attached claims.

[0110] Examples and Comparative Examples As shown in Tables 1 and 2 below, cleaning solution compositions were prepared by adjusting the types and contents of fluorinated compounds, polar aprotic solvents, and cyclic amide compounds. The content of each component is expressed as a weight percent of the total weight of the cleaning solution composition.

[0111] [Table 1]

[0112] [Table 2]

[0113] A-1: Tetrabutylammonium bifluoride (TBAF·HF) A-2: Tetrabutylammonium fluoride trihydrate (TBAF) A-3: Benzyltetramethylammonium fluoride hydrate (BTMAF) A-4: Tetrabutylphosphonium fluoride A-5: Tributylsulfonium fluoride B-1: Diethylacetamide B-2: Diethylformamide B-3: Ethylpyrrolidone B-4: Gamma-butyrolactone B-5: Triethyl phosphate B-6: Dimethylpropanamide B-7: Pyridine B-8: Ethylpyrrolidone B-9: Triglyme B-10: Dimethyl sulfoxide B-11:3-Pentanon B-12:3-Octanoon B-13: Jig Lime C-1: ε-caprolactam C-2: N-methyl-ε-caprolactam C-3: γ-Valerolactam C-4: Isatin C-5: ω-heptalactam C-6: ω-octalactam D-1: Water D-2: Nitric Acid D-3: Tetramethylammonium hydroxide D-4: Hydrogen peroxide D-5: Isopropyl alcohol D-6: Acetic acid E-1: Hexane E-2: Ethanol

[0114] Experimental example The physical properties of the cleaning solution compositions of the examples and comparative examples were evaluated using the following method, and the results are shown in Table 3.

[0115] (1) Evaluation of the removal rate of the network silicone polymer A wafer coated with a cured silicone polymer to a thickness of 50 μm is placed in a 2 × 2 cm area. 2 Test specimens were prepared by cutting them to the specified size. The prepared test specimens were immersed in the cleaning solution compositions of the examples and comparative examples for 1 minute while stirring at 400 rpm at 25°C, washed with isopropyl alcohol (IPA), and then dried. After drying, the film thickness of the cured silicone polymer was measured using a scanning electron microscope (SEM). The removal rate was calculated using the following formula 1, and the removal rate was evaluated according to the evaluation criteria below.

[0116] [Formula 1] Removal rate (μm / min) = [50 (μm) - thickness after drying (μm)] / immersion time (min)

[0117] <Evaluation Criteria> ○:20μm / min or more △: 10 μm / min or more and less than 20 μm / min ×: Less than 10 μm / min

[0118] (2) Evaluation of the removeability of linear silicone polymers A mixture of polydimethylsiloxane prepolymer and a curing agent in a predetermined mass ratio is spin-coated onto a silicone wafer, resulting in a 2 x 2 cm area. 2Test specimens were prepared by cutting the wafers to the specified size. The prepared test specimens were immersed in the cleaning solution compositions of the examples and comparative examples for 1 minute while stirring at 400 rpm at 25°C, then washed with isopropyl alcohol (IPA) and dried. After drying, the residue on the wafer surface was observed using a scanning electron microscope (SEM) and evaluated according to the evaluation criteria below. <Evaluation Criteria> ○: No residue ×: Residue present

[0119] (3) Evaluation of corrosion of metal films 1) A wafer on which bump balls having a Sn-Ag / Ni / Cu structure are formed is 2 × 2 cm 2 Test specimens were prepared by cutting them to the specified size. The prepared test specimens were immersed in the cleaning solution compositions of the examples and comparative examples for 1 minute while stirring at 400 rpm at 25°C, washed with isopropyl alcohol (IPA), and then dried. After drying, the number of damaged bump balls was confirmed by SEM, and the corrosion of the metal film was evaluated according to the evaluation criteria below. <Evaluation Criteria> ○: Less than 5 items △: 5 or more but less than 20 ×: 20 or more

[0120] 2) The wafers, on which copper thin films, tin thin films, or aluminum thin films have been formed by the sputtering process, are then cut to a size of 2 × 2 cm. 2 Test specimens were prepared by cutting them to the specified size. The prepared test specimens were immersed in the cleaning solution compositions of the examples and comparative examples for 1 minute while stirring at 400 rpm at 25°C, washed with isopropyl alcohol (IPA), and then dried. After drying, surface discoloration and morphological changes were observed under an optical microscope, and the corrosion of the metal film was evaluated according to the evaluation criteria below. <Evaluation Criteria> ○: No changes or discoloration in surface morphology. △: Surface morphological changes or discoloration present. ×: Surface morphological changes and discoloration present.

[0121] [Table 3]

[0122] Referring to Table 3, selective cleaning of silicone polymers was achieved using the cleaning solution compositions of the examples. Specifically, network or linear silicone polymers were rapidly and completely removed from the wafer surface using the cleaning solution compositions of the examples. Furthermore, bump balls were not damaged after cleaning with the cleaning solution compositions, and metal films containing copper, tin, aluminum, etc., were not altered.

[0123] When the cleaning solution compositions of Comparative Examples 1 to 6, which did not contain cyclic amide compounds, were used, the silicone polymer was not completely removed, and the removal rate decreased. Furthermore, the cleaning solution compositions of Comparative Examples 1 to 6 corroded the metal surface and were unsuitable for use in wafer cleaning processes.

[0124] The cleaning solution compositions of Comparative Examples 7 and 8 contained non-polar or polar protic solvents that reduced the activity of fluorinated compounds and did not provide sufficient removal properties for silicone polymers. The cleaning solution composition of Comparative Example 9 did not contain fluorinated compounds and did not adequately remove silicone polymers.

Claims

1. A cleaning solution composition comprising a cyclic amide compound represented by the following chemical formula 1, a polar aprotic solvent, and a fluorine compound. 【Chemistry 1】 (In the above chemical formula 1, R １ These are hydrogen, a C1-C5 alkyl group, or a C2-C5 alkenyl group. R ２ and R ３ Any one of them is a C1-C15 alkylene group, a C2-C15 alkenylene group, a C3-C20 cycloalkylene group, a C3-C20 cycloalkenylene group, or a C6-C20 arylene group. R ２ and R ３ The other of either is a direct bond, a C1-C15 alkylene group, a C2-C15 alkenylene group, a C3-C20 cycloalkylene group, a C3-C20 cycloalkenylene group, a C3-C10 heteroarylene group, a C3-C10 heterocycloalkylene group, or a C6-C20 arylene group. m is either 0 or 1.

2. In the above chemical formula 1, R ２ The cleaning solution composition according to claim 1, wherein is a C3-C7 alkylene group or a C6-C9 arylene group.

3. In the above chemical formula 1, R １ The cleaning solution composition according to claim 1, wherein is a hydrogen atom, a methyl group, or a vinyl group.

4. The washing solution composition according to any one of claims 1 to 3, wherein the cyclic amide compound comprises at least one selected from the group consisting of γ-valerolactam, ε-caprolactam, N-methyl-ε-caprolactam, N-vinyl-ε-caprolactam, ω-heptalactam, ω-octaractam, glycyl-L-proline lactam, isatin, and vinlactam.

5. The cleaning solution composition according to any one of claims 1 to 3, wherein the content of the cyclic amide compound is 0.001% to 10% by weight relative to the total weight of the cleaning solution composition.

6. The washing solution composition according to any one of claims 1 to 3, wherein the polar aprotic solvent comprises at least one selected from the group consisting of linear amide solvents, amine solvents, ketone solvents, morpholine solvents, pyrrolidine solvents, pyrrolidone solvents, urea solvents, lactone solvents, sulfoxide solvents, phosphate solvents, oxazolidone solvents, piperazine solvents, and alkylene glycol alkyl ether solvents.

7. The cleaning solution composition according to any one of claims 1 to 3, wherein the content of the polar aprotic solvent is 88% to 99% by weight with respect to the total weight of the cleaning solution composition.

8. The cleaning solution composition according to any one of claims 1 to 3, wherein the fluorine-based compound comprises an ionic bond between a nitrogen-based cation, a phosphorus-based cation, or a sulfur-based cation, and a fluorine anion.

9. The cleaning solution composition according to claim 8, wherein the nitrogen-based cation comprises an ammonium-based cation to which three or more C1-C10 alkyl groups are bonded.

10. The cleaning solution composition according to any one of claims 1 to 3, wherein the fluorine-based compound is in hydrate form.

11. The cleaning solution composition according to any one of claims 1 to 3, wherein the fluorine-based compound comprises at least one selected from the group consisting of tetrabutylammonium bifluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetra-n-butylammonium fluoride hydrate, tetra-n-butylammonium fluoride trihydrate, benzyltrimethylammonium fluoride hydrate, tributylsulfonium fluoride, and tetrabutylphosphonium fluoride.

12. The cleaning solution composition according to any one of claims 1 to 3, wherein the content of the fluorine-based compound is 1% to 12% by weight relative to the total weight of the cleaning solution composition.

13. A cleaning solution composition according to any one of claims 1 to 3, which does not contain ammonium hydroxide compounds, metal hydroxides, alcohol compounds, carboxylic acid compounds, peroxide compounds, or inorganic acid compounds.

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