阅读说明：本技术 用于清除聚合物的组合物 (Composition for removing polymers ) 是由 房淳洪 崔庆默 姜韩星 于 2021-03-25 设计创作，主要内容包括：本发明公开了用于清除聚合物的组合物,所述组合物包含：氟化烷基化合物、极性非质子溶剂和胺化合物,其中,所述胺化合物包括非环状仲胺化合物或非环状叔胺化合物。(The present invention discloses a composition for removing polymer, the composition comprising: a fluorinated alkyl compound, a polar aprotic solvent, and an amine compound, wherein the amine compound comprises an acyclic secondary amine compound or an acyclic tertiary amine compound.)

1. A composition for removing a polymer, the composition comprising: a fluorinated alkyl compound, a polar aprotic solvent, and an amine compound, wherein the amine compound comprises an acyclic secondary amine compound or an acyclic tertiary amine compound.

2. The composition according to claim 1, wherein the amine compound is a compound represented by one of formula 1 to formula 3,

[ formula 1]

In formula 1, R₁And R₂Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms (C1 to C8),

[ formula 2]

In formula 2, R₃To R₅Each independently represents a toolLinear or branched alkyl having 1 to 8 carbon atoms (C1 to C8),

[ formula 3]

In formula 3, n represents a positive integer of 3,4, 5 and 6.

3. The composition of claim 1, wherein the fluorinated alkyl compound comprises one or more compounds represented by any one of formula 4-1 and formula 4-2,

[ formula 4-1]

In the formula 4-1, R₆To R₉Each independently represents an alkyl group having 3 to 10 carbon atoms (C3 to C10),

[ formula 4-2]

In the formula 4-2, R₁₀To R₁₂Each independently represents an alkyl group having 1 to 10 carbon atoms (C1 to C10).

4. The composition of claim 1, wherein the polar aprotic solvent comprises at least one solvent selected from the group consisting of: ketone-based solvents, acetate-based solvents, amide-based solvents, pyridine-based solvents, morpholine-based solvents, pyrrolidone-based solvents, urea-based solvents, phosphate-based solvents, sulfoxide-based solvents, nitrile-based solvents, carbonate-based solvents, oxazolidinone-based solvents, and piperazine-based solvents.

5. The composition of claim 1, wherein the amine compound comprises at least one compound selected from the group consisting of: tripropylamine, tributylamine, tripentylamine, triisobutylamine, dimethyloctylamine, diethylbutylamine, diisobutylamine, N, N, N ', N' -tetramethyl-1, 3-diaminopropane, N, N, N ', N' -tetramethyl-1, 4-diaminobutane, and N, N, N ', N' -tetramethyl-1, 6-diaminohexane.

6. The composition of claim 1, wherein the amine compound has a boiling point in the range of 140 ℃ to 300 ℃.

7. The composition of claim 1, wherein the composition is used to scavenge a silicone-based polymer.

8. The composition according to claim 1, wherein the composition comprises from 0.1% to 20% by weight of the fluorinated alkyl compound, from 60% to 99.89% by weight of the polar aprotic solvent and from 0.01% to 20% by weight of the amine compound, relative to the total weight of the composition.

Technical Field

The present invention relates to compositions for removing silicone polymers.

Background

In manufacturing a semiconductor device, after an electronic circuit and the like are formed on a front surface (hereinafter, referred to as a "circuit surface") of a semiconductor wafer (hereinafter, simply referred to as a "wafer"), there is a case where back grinding (which is a process of grinding a back surface of the wafer) is performed to reduce the thickness of the wafer. In this case, in order to protect the circuit surface of the wafer or prevent the wafer from moving, the support is generally adhered to the circuit surface of the wafer by an adhesive polymer (e.g., silicone polymer). The support adhered to the circuit surface of the wafer has the following advantages: the wafer thinned by back grinding is enhanced and allows the formation of a back electrode on the ground back surface of the wafer.

After performing back grinding and forming the back electrode, the support is removed from the circuit surface of the wafer, the adhesive polymer is peeled off, and the wafer is diced to produce semiconductor chips.

In recent years, a chip stacking technique employing a through electrode (for example, a through silicon electrode) as an electrode formed to extend through a wafer has been developed and used. According to the chip stacking technology, since electronic circuits of a plurality of chips are electrically connected by through electrodes instead of typical wires, it is possible to achieve high-density integration and high-speed operation of the electronic circuits. When such a chip stacking technique is used, backgrinding is often performed to reduce the thickness of an assembly in which a plurality of chips are stacked. Thus, the use of supports and adhesive polymers is increasing.

With respect to this problem, the support is generally adhered to the circuit surface of the wafer by an adhesive polymer, and then the adhesive polymer is thermally cured to firmly adhere the support to the wafer. Therefore, when the adhesive polymer is peeled off, the cured adhesive polymer may remain on the circuit surface of the wafer. Therefore, there is a need for a means to effectively remove the cured adhesive polymer remaining on the circuit surface of the wafer. In addition, when removing the adhesive polymer, there is a problem in that a metal film or a bump ball (bump ball) may be damaged due to metal corrosion.

Patent document 1 discloses a composition for removing an adhesive polymer. However, the composition has a problem in that the removal rate for the network polymer is slow.

Documents of the prior art

Patent document

(patent document 1) Korean patent application publication No.10-2014-0060389

Disclosure of Invention

The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a composition for removing a polymer, which can effectively and rapidly remove an adhesive polymer remaining on a circuit surface of a wafer in a semiconductor device manufacturing process without causing metal corrosion.

Effects, features and objects of the present invention are not limited to those described above, and other effects, features and objects not mentioned above will be clearly understood by those of ordinary skill in the art from the following description.

To achieve the object of the present invention, there is provided a composition for removing a polymer, the composition comprising a fluorinated alkyl compound, a polar aprotic solvent, and an amine compound. The amine compound includes an acyclic secondary amine compound or an acyclic tertiary amine compound.

In accordance with the present invention, a polymer scavenging composition is provided that is capable of increasing the polymer scavenging rate by including a non-cyclic secondary or non-cyclic tertiary amine. In particular, the polymer removing composition of the present invention can remove the silicone-based polymer at a high speed and can minimize damage to a metal film or a stud ball by preventing metal corrosion.

Detailed Description

The present invention relates to a polymer removing composition comprising a fluorine compound, a solvent and an amine compound. The fluorine compound is a fluorinated alkyl compound, the solvent is a polar aprotic solvent, and the amine compound is an acyclic secondary amine compound or an acyclic tertiary amine compound.

In the present invention, the alkyl group means a hydrocarbon group bonded to a single bond.

< composition for removing Polymer >

According to the present invention, a composition for removing a polymer comprises a fluorinated alkyl compound, a polar aprotic solvent, and an amine compound. The composition may further comprise other additives and may be used to scavenge silicone polymers.

The polymer to be removed with the composition is not particularly limited, but is preferably a silicone polymer. Specifically, the silicone polymer includes linear polymers and network polymers. For example, silicone polymers include polyorganosiloxane-based resins that form network polymers upon curing, as well as linear non-reactive polydimethylsiloxane polymers.

In particular, the composition of the present invention has the advantage of removing not only linear polymers but also network polymers, since the fluorinated alkyl compound decomposes and dissolves the silicone polymer.

According to the present invention, since the amine compound adjusts the pH of the composition to a suitable level, the effect of preventing metal corrosion can be obtained during polymer removal. Therefore, damage to the metal film or the convex ball can be prevented. In particular, the composition can protect metals (such as Sn, Sn/Ag alloys, and Sn/Au alloys) by preventing corrosion of the metals. In this case, the metal that can be protected is not limited thereto.

Furthermore, the polymer-scavenging composition according to the present invention does not contain intentionally added water. Preferably, the polymer-scavenging composition is free of water. However, if desired, a hydrate of the fluorinated alkyl compound may be used. In this case, the polymer-removing composition may contain a small amount of water. In this case, water may be contained in the composition in an amount of less than 4% by weight, relative to the total weight of the composition. When the content of water exceeds this range, polymer scavenging property decreases and metal corrosion increases.

Further, it is preferable that the polymer removing composition according to the present invention does not contain a compound having a hydroxyl (-OH) group, such as an alcohol-based compound, in its molecular structure. When a compound has a hydroxyl group in its molecular structure, the hydroxyl group suppresses the activity of the fluorine compound, and the silicone resin has a problem of poor cleaning properties.

(A) Fluorinated alkyl compounds

The polymer removing composition according to the present invention comprises a fluorinated alkyl compound. Fluorinated alkyl compounds reduce molecular weight by breaking the ring of a polymer (e.g., a silicone polymer).

In the present invention, an example of the fluorinated alkyl compound is alkylammonium fluoride. Specifically, examples of the fluorinated alkyl compound include one or more compounds represented by formula 4-1 or formula 4-2.

[ formula 4-1]

In the formula 4-1, R₆To R₉Each being an alkyl group having 3 to 10 carbon atoms (C3 to C10). When R is₆To R₉Each of which is an alkyl group having two or less carbon atoms (C2 or less), precipitation occurs immediately after mixing or after a certain period of time has elapsed since the solubility of the fluorine compound in the solvent is lowered.

[ formula 4-2]

In the formula 4-2, R₁₀To R₁₂Each is an alkyl group having 1 to 10 carbon atoms (C1 to C10).

For example, as the alkyl fluoride compound, one or more compounds selected from tetrabutylammonium difluoride (TBAF · HF), tetrabutylammonium fluoride (TBAF), tetraoctylammonium fluoride (TOAF), and benzyltrimethylammonium fluoride (BTMAF) are used alone or in combination.

When the alkylammonium fluoride exists in the form of a hydrate, examples of the alkylammonium fluoride include tetra-n-butylammonium fluoride hydrate, tetra-n-butylammonium fluoride trihydrate, benzyltrimethylammonium fluoride hydrate, and the like.

The fluorinated alkyl compound is contained in an amount of 0.1 to 20% by weight, preferably 0.5 to 17% by weight, relative to the total weight of the composition of the scavenging polymer. When the fluorine compound is contained in an amount of less than 0.1% by weight, there is a problem that the polymer (silicone resin) adhered to the electronic part cannot be effectively removed. On the other hand, when the fluorine compound is contained in an amount of 20% by weight or more and it is present in the form of a hydrate-type alkylammonium fluoride, the water content increases, thereby deteriorating the effect of removing a polymer (such as a silicone resin). In addition, the metal film is corroded due to the excessive fluoride.

(B) Polar aprotic solvent

The polymer scavenging composition according to the present invention comprises a polar aprotic solvent. The polar aprotic solvent swells the silicone polymer and dissolves the fluorine compound and the decomposed silicone polymer.

As a generally known solvent, water and alcohol-based compounds (e.g., diethylene glycol monomethyl ether, ethylene glycol, isopropyl alcohol, etc.) have difficulty in removing polymers due to hydrogen bonding with fluoride ions. Thus, preferably, the solvent in the polymer removing composition according to the present invention does not comprise a water-or alcohol-based compound.

The polar aprotic solvent includes at least one solvent selected from the group consisting of: ketone-based solvents, acetate-based solvents, amide-based solvents, pyridine-based solvents, morpholine-based solvents, pyrrolidone-based solvents, urea-based solvents, phosphate-based solvents, sulfoxide-based solvents, nitrile-based solvents, carbonate-based solvents, oxazolidinone-based solvents, and piperazine-based solvents.

Specifically, examples of the ketone-based solvent include compounds represented by formula 5-1:

[ formula 5-1]

In the formula 5-1, R₁₃And R₁₄Each independently a linear or branched aliphatic hydrocarbon having 1 to 18 carbon atoms (C1 to C18), and R₁₃And R₁₄The total number of carbon atoms of (a) is preferably 2 or more and less than 30.

Examples of the ketone solvent include 2-heptanone, 3-heptanone, 4-heptanone, 3-pentanone, 2-hexanone, 3-hexanone, 4-methyl-2-pentanone, 5-methyl-2-hexanone, and 2, 6-dimethyl-4-hexanone, but are not limited thereto.

Specifically, examples of the acetate-based solvent include methyl acetate, Ethyl Acetate (EA), propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate (amyl acetate), isoamyl acetate, octyl acetate, benzyl acetate, phenyl acetate, ethoxyethyl acetate, methoxybutyl acetate (MBA), Propylene Glycol Monomethyl Ether Acetate (PGMEA), vinyl acetate, or Ethyl Ethoxypropionate (EEP), and the like, but are not limited thereto.

Specifically, examples of the amide-based solvent include, but are not limited to, N-dimethylacetamide, N-diethylacetamide, N-dipropylacetamide, N-ethyl-N-methylacetamide, N-dimethylpropionamide (N, N-dimethylpropionamide), N-dimethylbutanamide, N-dimethylpentanamide, N-dimethylpropionamide (N, N-dimethylpropionamide), N-diethylpropionamide, and N, N-dibutylpropionamide.

Specifically, examples of the pyridine-based solvent include compounds represented by formula 5-2:

[ formula 5-2]

In the formula 5-2, R₁₅To R₁₇Each independently hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms (C1 to C10), a halogen (e.g., F, Cl, Br, I), an aldehyde group (-CHO), an aldehyde group (-COCH)₃) Alkoxy having 1 to 4 carbon atoms (C1 to C4), vinyl, ethynyl, cyano (-CN) or methylthio (-SCH)₃)。

Examples of the pyridine solvent include pyridine, 2-methylpyridine, 3-methylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-isopropylpyridine, 4-pentylpyridine, 2, 3-dimethylpyridine, 2, 4-dimethylpyridine, 2, 5-dimethylpyridine, 3, 4-dimethylpyridine, 3, 5-dimethylpyridine and 2,4, 6-trimethylpyridine, but are not limited thereto.

Specifically, examples of the morpholine solvent include compounds represented by formulas 5 to 3:

[ formulas 5 to 3]

In the formula 5-3, R₁₈Is hydrogen, a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms (C1 to C6), a vinyl group, a cyano group (-CN), an aliphatic hydrocarbon group having 1 to 4 carbon atoms (C1 to C4) and substituted with a tertiary amine, or a phenyl group or a pyridyl group substituted with an alkyl group having 1 to 4 carbon atoms (C1 to C4), a cyano group (-CN), a halogen group (e.g., F, Cl, Br or I), or an aldehyde group (-CHO); x is oxygen or-NR₁₉-; and R is₁₉Is an aliphatic hydrocarbon group having 1 to 4 carbon atoms (C1 to C4).

Examples of the morpholine-based solvent include, but are not limited to, N-methylmorpholine, N-ethylmorpholine, N-arylmorpholine, N-butylmorpholine, N-isobutylmorpholine, and the like.

Specifically, examples of the pyrrolidone-based solvent include, but are not limited to, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), and N-vinylpyrrolidone (NVP).

Specifically, examples of the urea-based solvent include compounds represented by formulas 5 to 4:

[ formulas 5 to 4]

In the formulae 5 to 4, X is oxygen or-NR₁₉-, and R₁₉And R₂₀Each independently is a linear, branched or cyclic aliphatic hydrocarbon group having 1 to 6 carbon atoms (C1 to C6), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms (C1 to C4) and substituted with a vinyl group, a phenyl group, an ethynyl group, a methoxy group or a dimethylamino group.

Examples of the urea-based solvent include tetramethylurea, tetraethylurea, tetrabutylurea, and the like, but are not limited thereto.

Specifically, examples of the phosphate ester-based solvent include compounds represented by formulas 5 to 5:

[ formulas 5 to 5]

In the formula 5-5, R₂₁To R₂₃Each independently is a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms (C1 to C8), a divalent aliphatic hydrocarbon group having 3 to 8 carbon atoms (C3 to C8) and forming a ring with the adjacent oxygen, a phenyl group unsubstituted or substituted with an aliphatic hydrocarbon group having 1 to 4 carbon atoms (C1 to C4), an aliphatic hydrocarbon group having 2 to 4 carbon atoms and substituted with a halogen (e.g., F, Cl, Br, or I), or a phenyl group substituted with a halogen. Group "-CH-contained in a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms (C1 to C8)₂- "may be substituted by an oxygen atom.

Examples of the phosphate ester-based solvent include triethyl phosphate, tributyl phosphate, tripentyl phosphate, triaryl phosphate, and the like, but are not limited thereto.

Specifically, examples of the sulfoxide-based solvent include dimethyl sulfoxide (DMSO), dibutyl sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide, and tolyl sulfoxide, but are not limited thereto.

Specifically, examples of the nitrile-based solvent include propionitrile, butyronitrile, isobutyronitrile, acetonitrile, trimethylacetonitrile, and phenylacetonitrile, but are not limited thereto.

Specifically, examples of the carbonate-based solvent include dimethyl carbonate (DMC), diethyl carbonate, diphenyl carbonate, dibenzyl carbonate, ethylene carbonate, Propylene Carbonate (PC), and vinylene carbonate, but are not limited thereto.

Specifically, examples of the oxazolidinone-based solvent include 2-oxazolidinone, 3-methyl-2-oxazolidinone, and the like, but are not limited thereto.

Examples of the piperazine-based solvent include dimethylpiperazine, dibutylpiperazine, and the like, but are not limited thereto.

On the other hand, according to the present invention, the polar aprotic solvent does not include the acyclic tertiary amine described later.

The polar aprotic solvent is included in an amount of 60% to 99.89% by weight, preferably 68% to 99.45% by weight, relative to the total weight of the composition of scavenging polymer. When the polar aprotic solvent is contained in an amount of less than 60% by weight, there is a problem that the metal film is corroded. On the other hand, when the polar aprotic solvent is contained in an amount exceeding 99.89% by weight, there is a problem that the silicone resin adhering to the electronic component cannot be effectively removed.

(C) Amine compound

The polymer scavenging composition according to the present invention comprises an amine compound, and the amine compound is an acyclic secondary amine compound or an acyclic tertiary amine compound. The amine compound promotes the swelling of the silicone polymer and improves the solubility of the fluorinated alkyl compound, thereby increasing the rate of removal of the silicone polymer. In the present invention, the amine compound exhibits an anti-corrosion effect by adjusting the pH of the polymer-removing composition to an appropriate level.

The amine compound having a specific structure is suitably used in terms of maximizing the functional effect of scavenging the amine compound in the polymer composition. For example, as the number of carbon atoms in the alkyl group of the amine increases, the effect of swelling the silicone polymer increases, and as the number of carbon atoms in the alkyl group of the amine decreases, the effect of improving the solubility of the fluorinated alkyl compound increases. In addition, the better the ionization of the fluorinated alkyl compound, the more corrosion occurs. To obtain complementary effects, amine compounds are used. That is, the amine compound improves polymer removal and reduces corrosion of metals. Specifically, an amine compound having a specific structure described below is preferably used.

Specifically, examples of the amine compound used in the present invention include compounds represented by any one of formula 1 to formula 3.

[ formula 1]

In formula 1, R₁And R₂Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms (C1 to C8). When R is₁And R₂When the same, R₁And R₂Preferably represents an alkyl group having 4 or more carbon atoms.

More preferably, R₁And R₂Each independently represents a linear or branched alkyl group having 2 to 8 carbon atoms (C2 to C8). When R is₁And R₂When the same, R₁And R₂Preferably represents a linear or branched alkyl group having 4 to 8 carbon atoms (C4 to C8).

[ formula 2]

In formula 2, R₃To R₅Each represents an alkyl group having 1 to 8 carbon atoms (C1 to C8).

[ formula 3]

In formula 3, n is a positive integer of 3,4, 5 and 6.

The amine compound is preferably an amine compound having a boiling point of 140 ℃ or higher, more preferably an amine compound having a boiling point in the range of 140 ℃ to 300 ℃. When the amine compound satisfies one of formulae 1 to 3 and the boiling point is 140 ℃ or more, the polymer-removing composition according to the present invention can be easily applied to a device manufacturing process since volatile components are minimized. When the boiling point of the amine compound is 140 ℃ or higher, not only the effect of improving the polymer scavenging property but also the effect of preventing metal corrosion can be expected. When the boiling point of the amine compound is lower than 140 ℃, a great improvement in polymer scavenging performance is expected, but the effect of preventing metal corrosion is insignificant. Therefore, it is difficult to obtain both the effect of improving the polymer removing performance and the effect of preventing metal corrosion.

For example, the amine compound includes one or more compounds selected from the group consisting of: tripropylamine (boiling point: 158 ℃), tributylamine (boiling point: 215 ℃), tripentylamine (boiling point: 242 ℃), triisobutylamine (boiling point: 191 ℃), dimethyloctylamine (boiling point: 192 ℃), diethylbutylamine (boiling point: 141 ℃), diisobutylamine (boiling point: 141 ℃), N, N, N ', N' -tetramethyl-1, 3-diaminopropane (boiling point: 144 ℃), N, N, N ', N' -tetramethyl-1, 4-diaminobutane (boiling point: 169 ℃) and N, N, N ', N' -tetramethyl-1, 6-diaminohexane (boiling point: 209 ℃).

The amine compound is contained in an amount of 0.01% to 20%, preferably 0.05% to 15% by weight relative to the total weight of the composition for removing the polymer. When the amine compound is contained in an amount of less than 0.01%, it is difficult to expect an increase in the removal rate. On the other hand, when the content of the amine compound exceeds 20% by weight, the polymer swelling effect does not increase in proportion to the amount of the amine compound contained, and metal corrosion increases.

(D) Additive agent

In addition to the above components, the polymer scavenging composition according to the present invention optionally comprises other components such as corrosion inhibitors and surfactants commonly used in the art.

The corrosion inhibitor is effective for inhibiting corrosion of the metal-containing primary film during removal of the resin. Corrosion inhibitors are commercially available from various sources and can be used without further purification.

Surfactants are used to enhance the polymer removal effect. For example, anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Among them, a nonionic surfactant which has excellent wettability and generates a small amount of bubbles is preferably used. One or more surfactants selected from these surfactants may be used alone or in combination.

The invention also provides a method of removing polymer from a device using the polymer removing composition according to the invention. All the details described in connection with the composition for removing polymers according to the present invention can be applied to the polymer removal method according to the present invention. Hereinafter, although a redundant detailed description will not be given, these may be applied to the polymer removing method according to the present invention.

Specifically, the polymer removal method is a method for removing a polymer (such as a silicon adhesive) used in a wafer thinning process. The wafer thinning process includes the steps of forming a silicone release layer and a silicone adhesive layer between the carrier wafer and the device wafer and thinning the device wafer. The silicone release layer serves as a release location where the carrier wafer is removed without damaging the device wafer. The silicone adhesive bonds the device wafer to the carrier wafer and undergoes a curing process. After such a process, the cured polymer is removed using the polymer removing composition according to the present invention.

The present invention will be described in more detail with reference to examples described below. The examples are intended to describe the present invention in more detail, but the scope of the present invention is not limited to these examples.

Examples and comparative examples: preparation of polymer scavenging compositions

Compositions for scavenging polymers were prepared according to the ingredients and compositional ratios listed in tables 1 and 2.

[ Table 1]

[ Table 2]

< fluorine Compound >

(A-1) TBAF. HF: tetrabutylammonium difluoride;

(A-2) TBAF: tetrabutylammonium fluoride;

(A-3) BTMAF: benzyltetramethylammonium fluoride;

(A-20) ammonium fluoride (NH)₄HF₂)

< solvent >

(B-1) 2-heptanone; (B-2) N, N-diethylacetamide;

(B-3) N, N-dimethylpropionamide (N, N-dimethylpropanamide); (B-4) N-ethylpyrrolidone;

(B-5) N-methylmorpholine; (B-6) n-butyl acetate;

(B-7) PGMEA: propylene glycol monomethyl ether acetate;

(B-8) 4-methylpyridine; (B-9) dimethylpiperazine;

(B-10) triethyl phosphate; (B-11) tetraethylurea;

(B-20) ethylene glycol; (B-21) Isopropanol

(B-22) water; (B-23) diethylene glycol monomethyl ether

< amine Compound >

(C-1) tripropylamine (bp. point 158 ℃ C.);

(C-2) diisobutylamine (bp 141 ℃ C.);

(C-3) tributylamine (bp 215 ℃ C.);

(C-4) Dimethyloctylamine (bp 192 ℃ C.);

(C-5) N, N, N ', N' -tetramethyl-1, 3-diaminopropane (boiling point 144 ℃ C.);

(C-6) triethylamine (bp 89 ℃);

(C-20) octylamine (bp 176 ℃ C.);

(C-21) monoethanolamine (bp 174 ℃ C.);

(C-22) hydroxylamine (boiling point 58 ℃ C.);

(C-23) aqueous tetramethylammonium hydroxide (20%) (bp 102 ℃ C.)

(C-24) Dipropylamine

(C-25) N-methylbutylamine

(test example 1) evaluation of Polymer Clearance 1-network Polymer

To evaluate the removability of the network polymer, a wafer coated with the cured silicone polymer to a thickness of 80 μm was cut into pieces having a size of 2cm × 2cm, and the pieces were used as samples. Solutions of each composition according to examples and comparative examples were heated to 25 ℃ and rotated at 400 rpm. The prepared samples were soaked in each composition solution for 1 minute, washed with isopropyl alcohol (IPA), and dried. The film thickness of the cured silicone polymer of each sample was measured by Scanning Electron Microscopy (SEM) prior to immersing the sample in the composition solution. After soaking, washing and drying the samples, the thickness of the residual silicone resin in each sample was measured with a Scanning Electron Microscope (SEM), and the removal rate of each composition solution was calculated and summarized in tables 3 and 4.

Clearance rate (μm/min) ═ thickness before test (μm) -thickness after test (μm) ]/test time (min)

(test example 2) evaluation of Polymer cleanability 2-Linear PDMS

In order to evaluate the cleanability of linear Polydimethylsiloxane (PDMS), a mixture obtained by mixing a prepolymer of Polydimethylsiloxane (PDMS) and a curing agent in a predetermined mass ratio was spin-coated on a silicon wafer and cut into small pieces having a size of 2cm × 2cm, and the small pieces were used as samples. The composition solutions according to examples and comparative examples were heated to 25 ℃ and rotated at 400 rpm. The samples were soaked in each composition solution for 1 minute, washed with IPA, and dried. After the test, the residue on the surface of each sample was observed with an optical microscope and SEM. The presence or absence of residue on each sample is indicated in tables 3 and 4.

O: absence/X: exist of

(test example 3) evaluation of Metal Corrosion of 1-convex ball

To evaluate the metal corrosion, a wafer having 1011 convex balls made of Sn, Sn/Ag alloy, or Sn/Au alloy was cut into small pieces having a size of 2cm × 2cm, and the small pieces were used as samples. The prepared samples were soaked in each composition solution according to examples and comparative examples for 30 minutes while heating the composition solution to 25 ℃ and rotating at 400rpm, washed with IPA, and dried. Each sample was observed with SEM. The number of damaged domes in each sample was counted and summarized in tables 3 and 4.

(test example 4) evaluation of Metal Corrosion 2-Metal film

The wafer coated with the aluminum thin film was cut into small pieces having a size of 2cm × 2cm, and the small pieces were used as samples. Solutions of each composition according to examples and comparative examples were heated to 25 ℃ and rotated at 400 rpm. The prepared samples were soaked in each composition solution for 10 minutes, washed with isopropyl alcohol (IPA), and dried. After washing, the films on the respective samples were inspected for defects with SEM, and the results are summarized in tables 3 and 4 according to the following criteria.

Good: no surface morphological change or discoloration was observed.

The following happens: surface morphological changes and discoloration were observed.

[ Table 3]

[ Table 4]

Referring to table 3, the polymer-removing compositions according to the present invention (examples 1 to 21) exhibited high removal rates of 23 μm/min or more for the network-silicone based polymers and excellent removal performance for the linear silicone based polymers. In addition, the compositions according to the invention exhibit a good anti-corrosive action. When the amine compound having a low boiling point was used (example 21), or when the amine compound was added in excess (example 20), the performance was slightly lowered, but was significantly better than that of the comparative example.

On the other hand, referring to Table 4, comparative example 7 and comparative examples 10 to 12, in which the amine compound according to the present invention was not used, exhibited a scavenging rate of 12 μm/min or less for the network polymer. That is, the removal rate was significantly reduced and the corrosion of the metal was also significantly increased, compared to the case of using the composition according to the example.

In addition, even when the amine compound according to the present invention was used, when water or an alcohol-based compound was used as a solvent (comparative examples 5 and 6), it was confirmed that polymer removal was difficult and metal corrosion was very high. In comparative examples 8 and 9, both using a protic solvent, the polymer removal rate was low, and residues remained after removing the polymer.

On the other hand, when the polar aprotic solvent was used alone, the polymer was not purged (comparative example 1 and comparative example 2). When ammonium fluoride was used as the fluorine compound (comparative example 3), precipitation occurred during the preparation of the composition, so that evaluation could not be performed. In addition, in comparative examples 13 and 14, which respectively used dipropylamine and N-methylbutylamine as amine compounds, the removal rate of the network polymer was reduced to 20 μm/min or less, and 40 or more of the 1011 convex balls made of Sn, Sn/Ag alloy, or Sn/Au alloy were damaged.