KR102265415B1 - Curable polymer stripping composition - Google Patents

Abstract

The present invention is a cation stabilizer 0.01 to 10% by weight of a fluorine compound 0.1 to 30% by weight; And it relates to a cured polymer stripper composition comprising a polar aprotic solvent as the balance, and the cleaning rate can be improved by adding a cationic stabilizer.

Description

Curable polymer stripping composition {Curable polymer stripping composition}

The present invention relates to a cured polymer stripper composition.

In the manufacturing process of a semiconductor device, after forming an electronic circuit on the surface of a semiconductor wafer (hereinafter simply referred to as "wafer"), the back surface grinding (so-called back grinding) of the wafer is performed in order to reduce the thickness of the wafer. There are cases. In this case, in order to protect the wafer circuit surface, fix the wafer, and the like, a support is usually attached to the circuit surface of the wafer via a silicon-based resin. If the support is attached to the circuit surface of the wafer, the wafer, which has become thinner after grinding the back surface of the wafer, can be reinforced, and a back electrode or the like can be formed on the ground surface of the wafer.

When the process of grinding the back surface of the wafer, forming the back electrode, etc. is completed, the support is removed from the circuit surface of the wafer, the silicon-based resin attached to the electronic component is peeled off and removed, and the wafer is cut to manufacture a chip.

Meanwhile, in recent years, a chip stacking technique using a through electrode (eg, a silicon through electrode) installed through a wafer has been developed. According to this chip stacking technique, since the electronic circuits of a plurality of chips are electrically connected using through-electrodes instead of conventional wires, high-integration of chips and high-speed operation can be achieved. When this chip stacking technique is used, the back surface of the wafer is often ground in order to reduce the thickness of the aggregate on which a plurality of chips are stacked, and therefore, the case of using a silicon-based resin for a support or an electronic component increases.

However, in general, after attaching a support to the circuit surface of the wafer via a silicon-based resin attached to an electronic component, thermosetting is performed to firmly attach the wafer to the support. Therefore, when the silicone-based resin adhered to the electronic component is peeled off, the silicone-based resin adhered to the cured electronic component may remain on the circuit surface of the support and the wafer. Therefore, there is a need for a means for efficiently removing the silicone-based resin adhering to the cured electronic component remaining on the support and the wafer circuit surface.

Korean Patent Application Laid-Open No. 10-2014-0060389 discloses a composition for removing an adhesive polymer including alkylammonium fluoride and a polar aprotic organic solvent. Although the prior patent presents a technology that removes the adhesive polymer very effectively and does not corrode the circuit on the wafer circuit surface, the feature of improving the cleaning speed by applying a new composition is not satisfied.

Korean Patent Publication No. 10-2014-0060389

An object of the present invention is to provide a cured polymer stripper composition capable of improving the cleaning rate by adding a cationic stabilizer.

The cured polymer stripper composition of the present invention for achieving the above object is characterized in that it contains 0.01 to 10% by weight of a cation stabilizer, 0.1 to 30% by weight of a fluorine compound, and a polar aprotic solvent as the balance.

The cured polymer stripper composition according to the present invention can improve the cleaning rate by stabilizing the cations due to the above combination.

The cured polymer stripper composition according to the present invention includes a cationic stabilizer, a fluorine compound, and a polar aprotic solvent.

Hereinafter, each composition will be described in detail.

In the cured polymer stripper composition of the present invention, the cation stabilizer serves to stabilize the cation to improve the cleaning rate. The cation stabilizer forms a crown structure, and the inside of the ring is electron-rich and has a strong negative charge. Because of this negative charge, Crown Ether can easily act as a Lewis base (a substance that donates electrons), and can form a coordination bond with an electron-deficient metal ion. More specifically, since there is a space of a suitable size in the center of the large ring shape, alkali metal ions and organic cations such as amino acids and amines are introduced to form a clathrate compound between the oxygen atoms, thereby stabilizing the cations.

The cation stabilizer is preferably a crown ether (Crown Ether), for example, the cation stabilizer is 12-Crown 4-Ether, 15-Crown 5-Ether, 18-Crown 6-Ether, 24-Crown 8-Ether, It may be one selected from Benzo-12-crown 4-Ether, Benzo-15-crown 5-Ether, Dibenzo-15-crown 5-Ether, and Dibenzo-18-crown 6-Ether.

In the present invention, the cation stabilizer is preferably included in an amount of 0.01 to 10% by weight within 100% by weight of the total composition, more preferably 0.1 to 5% by weight. When the cation stabilizer is included in less than the above range, the cleaning rate may be slow, and on the contrary, when included in excess of the above range, the physical properties of the entire composition may be reduced.

In the cured polymer stripper composition of the present invention, the polar aprotic solvent serves to dissolve the fluorine compound. In particular, polar solvents are used because they stabilize the intermediate in the SN2 reaction.

In the present invention, the polar aprotic solvent is a ketone-based, acetate-based, amide-based, pyridine-based, morpholine-based, piperazine-based, pyrrolidone-based, urea-based, oxazolidinone-based, phosphate-based, sulfoxide-based, nitrate-based solvent. At least one selected from the group consisting of reel-based and carbonate-based solvents is used.

The type of the ketone-based solvent is not particularly limited, but preferably includes the following formula (1).

[Formula 1]

(In Formula 1,

R ₁ and R ₂ are each the same or different, a linear or branched aliphatic hydrocarbon having 1 to 18 carbon atoms, _{and the sum of carbon atoms of R 1} and R ₂ is 2 or more and less than 30.)

The type of the acetate-based solvent is not particularly limited, but methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, pentyl acetate, isopentyl acetate, octyl acetate, It is preferable to use at least one selected from the group consisting of benzyl acetate, phenyl acetate, ethoxyethyl acetate, methoxybutyl acetate, propylene glycol monomethyl ether acetate, vinyl acetate and ethyl ethoxy propionate.

The type of the amide-based solvent is not particularly limited, but at least one selected from the group consisting of dimethylformamide, dimethylpropanamide and dimethylbutanamide is preferably used.

The type of the pyridine-based solvent is not particularly limited, but preferably includes the following formula (2).

[Formula 2]

(In Formula 2,

R ₃ to R ₅ are each the same or different, hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, an aldehyde group, an acetaldehyde group, a cyanide group or a methylsulfide group .)

Accordingly, the pyridine-based solvent is pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-isopropylpyridine, 4-amylpyridine, 2,3-ruti. It may be at least one selected from the group consisting of din, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5-lutidine and 2,4,6-trimethylpyridine.

The type of the morpholine-based solvent is not particularly limited, but preferably includes the following formula (3).

[Formula 3]

(In Formula 3,

R ₆ is hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms, a cyanide group, a tertiary amine including an aliphatic hydrocarbon having 1 to 4 carbon atoms, an aliphatic hydrocarbon having 1 to 4 carbon atoms, a halogen, a cyanide group, or phenyl substituted with an aldehyde group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms, halogen, pyridine substituted with a cyanide group or an aldehyde group.)

The type of the piperazine-based solvent is not particularly limited, but preferably includes the following formula (4).

[Formula 4]

(In Formula 4,

R ₇ and R ₈ are each the same or different, hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms, a cyanide group, a tertiary amine including an aliphatic hydrocarbon having 1 to 4 carbon atoms, and 1 to 4 carbon atoms aliphatic hydrocarbon, halogen, phenyl substituted with a cyanide group or an aldehyde group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms, halogen, pyridine substituted with a cyanide group or an aldehyde group.)

The type of the pyrrolidone-based solvent is not particularly limited, but at least one selected from the group consisting of methylpyrrolidone, ethylpyrrolidone and vinylpyrrolidone is preferably used.

The type of the urea-based solvent is not particularly limited, but preferably includes the following formula (5).

[Formula 5]

(In Formula 5,

R ₉ and R ₁₀ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 6 carbon atoms, a phenyl group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms substituted with a methoxy group or a dimethylamino group.)

The type of the oxazolidinone-based solvent is not particularly limited, but preferably includes the following formula (6).

[Formula 6]

(In Formula 6,

R ₁₁ is an aliphatic hydrocarbon having 1 to 6 carbon atoms, a phenyl group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms substituted with a methoxy group or dimethylamino group.)

The type of the phosphate-based solvent is not particularly limited, but preferably includes the following formula (7).

[Formula 7]

(In Formula 7,

R ₁₂ to R ₁₄ are the same or different, each of which is a phenyl group substituted with a linear or branched aliphatic hydrocarbon having 1 to 8 carbon atoms, an alkoxy group having 3 to 8 carbon atoms, a phenyl group, an aliphatic hydrocarbon having 1 to 4 carbon atoms, or halogen It is an aliphatic hydrocarbon having 2 to 4 carbon atoms.)

Although the type of the sulfoxide-based solvent is not particularly limited, it is preferable to use at least one selected from the group consisting of dimethyl sulfoxide, dibutyl sulfoxide, diphenyl sulfoxide, dibenzyl sulfoxide and methylphenyl sulfoxide. .

Although the type of the nitrile-based solvent is not particularly limited, at least one selected from the group consisting of propionitrile, butyronitrile, isobutyronitrile, acetonitrile, trimethylacetonitrile and phenylacetonitrile is used. It is preferable to do

In addition, the carbonate-based solvent is not particularly limited in kind, but at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibenzyl carbonate, ethylene carbonate, propylene carbonate and vinylene carbonate is used. it is preferable

The polar aprotic solvent is included in the balance based on 100% by weight of the polymer stripper composition, and is preferably included in an amount of 70 to 99.9% by weight. If the polar aprotic solvent is included below the content range, there may be a problem in that the metal portion of the circuit surface of the substrate is corroded, and if it exceeds the content range, the physical properties of the entire composition may be reduced.

In the cured polymer stripper composition of the present invention, the fluorine compound breaks the ring of the silicone polymer, thereby reducing the molecular weight.

More specifically, since the bonding strength of Si-F is stronger than that of Si-O, an ammonium fluoride compound is used to break the Si-O bond of the silicone resin. In this compound, the fluorine anion _{performs a S N} 2 reaction attacking Si and the ammonium cation acts as a cation stabilizing the fluorine anion. However, the ammonium fluoride compound _{exists in the form of a hydrate (nH 2} O), and the number of the hydrates increases over time due to the high hydrophilicity of the nitrogen atom of the ammonium cation, and the moisture contained therein forms a strong hydrogen bond with the fluorine anion. By forming, the side effect of reducing the nucleophilicity of the fluorine anion is shown. Therefore, it is possible to reduce the moisture content in the silicone-based resin cleaning composition by using a fluorine compound including a sulfonium salt or a phosphonium salt having a stronger hydrophobicity instead of an ammonium salt. As a result, fewer HO-HF bonds are formed due to hydrogen bonding, and reduction in the nucleophilicity of the fluorine anion is suppressed, so that the cleavage reaction of the Si-O bond by the fluorine anion can proceed more effectively.

In order to satisfy the above-described characteristics, the fluorine compound of the present invention is preferably at least one selected from the group consisting of alkylammonium fluoride, alkylphosphonium fluoride and alkylsulfonium fluoride.

The alkylammonium fluoride preferably includes the following formula (8).

[Formula 8]

(In Formula 8,

Wherein m is an integer from 0 to 15, and n is an integer from 2 to 21.)

In addition, Chemical Formula 8 is preferably at least one selected from the group consisting of the following Chemical Formulas 9 to 14.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Formulas 9 to 14, p and q may each be an integer of 0 to 4.

The alkylammonium fluoride may be specifically, for example, tetrabutylammonium fluoride, tetrabutylammonium bifluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride, and tetraoctylammonium fluoride. .

The alkyl phosphonium fluoride preferably includes the following formula (15).

[Formula 15]

(In Formula 15,

R ₁₅ to R ₁₈ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 22 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.)

In addition, the alkylsulfonium fluoride preferably includes the following formula (16).

[Formula 16]

(In Formula 16,

R ₁₉ to R ₂₁ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 22 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.)

The fluorine compound is preferably included in an amount of 0.1 to 30 wt%, more preferably 1 to 20 wt%, based on the total weight of the cured polymer stripper composition. When the fluorine compound is included below the content range, a problem may occur that the cured polymer cannot be cleaned, and if the content exceeds the content range, a problem of corrosion of the metal part of the circuit surface of the substrate may occur. .

The cured polymer stripper composition of the present invention may further include components such as corrosion inhibitors and surfactants commonly used in this field in addition to the above components.

The corrosion inhibitor is used to effectively inhibit corrosion of the metal-containing lower layer when the resin is removed, and for example, catechol; (C _1-6 )alkylcatechol, such as methylcatechol, ethylcatechol and tert-butylcatechol; benzotriazole; hydroxyanisole; (C _1-10 )alkylbenzotriazole; hydroxy(C _1-10 )alkylbenzotriazole; 2-mercaptobenzoimidazole; gallic acid; gallic acid esters such as methyl gallate and propyl gallate; and tetra(C _1-4 )alkylammonium silicate, such as tetramethylammonium silicate, and the like. Such corrosion inhibitors are generally commercially available from a variety of sources, for example, Aldrich Chemical Company (Milwaukee, Wisconsin) and can be used without further purification.

The surfactant may be used to enhance cleaning properties. For example, anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Among them, it is particularly preferable to use a nonionic surfactant having excellent wettability and less foaming.

The nonionic surfactant is specifically, polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene polyoxybutylene alkyl ether type, polyoxyethylene alkylamino ether type, polyoxyethylene alkylamido ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, glycerin fatty acid ester type, alkylolamide type and glycerin ester type, etc., and these are one type or two or more types. can be mixed and used.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Examples 1 to 5 and Comparative Examples 1 to 4

A cured polymer stripper composition was prepared by adding the components and compositions (wt%) of Table 1 below.

Furtherance
(weight%) 15-Crown 5-Ether 18-Crown 6-Ether DMF Pyridine NMM n-BA MEK DMAc DBU TBAF Example 1 One 96 3 Example 2 One 96 3 Example 3 One 96 3 Example 4 One 96 3 Example 5 One 92 4 3 Comparative Example 1 93 4 3 Comparative Example 2 93 4 3 Comparative Example 3 97 3 Comparative Example 4 97 3 - DMF: Dimethylformamide
-NMM: N-methylmorpholine
- n-BA: n-Butylacetate
- MEK: Methylethyl Ketone
- DMAc: N,N-Dimethylacetamide
- DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene
- TBAF: Tetrabutylammonium Fluoride

(1) Cured silicone cleaning speed evaluation

A wafer coated with a cured silicone polymer having a thickness of 80 μm was cut into a size of 2X2 cm 2 , and the prepared sample was immersed for 1 minute while rotating the composition solution at 25° C. at 350 rpm, followed by IPA cleaning and drying. Then, after evaluation, the film thickness of the cured silicone polymer was measured by SEM.

Table 2 below shows the evaluation results of the dissolution rate of the cured cured silicone tested under the same conditions as described above.

Cured silicone dissolution rate (㎛/min) Example 1 19.0 Example 2 18.7 Example 3 21.2 Example 4 21.0 Example 5 21.5 Comparative Example 1 17.3 Comparative Example 2 16.8 Comparative Example 3 16.0 Comparative Example 4 15.2

Referring to Table 2, it can be seen that in Examples 1 to 5 using Crown Ether as an additive, the dissolution rate of cured silicone increased to an average of 20.28 μm/min.

However, it can be seen that the dissolution rate is very slow in Comparative Examples 1 to 2 using the amine-based additive and Comparative Examples 3 to 4 in which the Crown Ether is not used.

Claims (14)

Cationic stabilizer 0.01 to 10% by weight
0.1 to 30% by weight of a fluorine compound; and
A cured polymer stripper composition comprising the balance of a polar aprotic solvent. According to claim 1,
The polar aprotic solvent is
Characterized in that it is one selected from ketone-based, acetate-based, amide-based, pyridine-based, morpholine-based, pyrrolidone-based, urea-based, phosphate-based, sulfoxide-based, nitrile-based, piperazine-based, oxazolidinone-based and carbonate-based types A cured polymer stripper composition comprising 3. The method of claim 2,
The ketone-based solvent is a cured polymer stripper composition comprising the following formula (1):
[Formula 1]

(In Formula 1,
R ₁ and R ₂ are each the same or different, a linear or branched aliphatic hydrocarbon having 1 to 18 carbon atoms, _{and the sum of carbon atoms of R 1} and R ₂ is 2 or more and less than 30.) 3. The method of claim 2,
The pyridine-based solvent is a cured polymer stripper composition, characterized in that it comprises the following formula 2:
[Formula 2]

(In Formula 2,
R ₃ to R ₅ are each the same or different, hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, an aldehyde group, an acetaldehyde group, a cyanide group or a methylsulfide group .) 3. The method according to claim 2,
The morpholine-based solvent is a cured polymer stripper composition comprising the following formula (3):
[Formula 3]

(In Formula 3,
R ₆ is hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms, a cyanide group, a tertiary amine including an aliphatic hydrocarbon having 1 to 4 carbon atoms, an aliphatic hydrocarbon having 1 to 4 carbon atoms, a halogen, a cyanide group, or phenyl substituted with an aldehyde group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms, halogen, pyridine substituted with a cyanide group or an aldehyde group.) 3. The method according to claim 2,
The piperazine-based solvent is a cured polymer stripper composition, characterized in that it comprises the following formula (4):
[Formula 4]

(In Formula 4,
R ₇ and R ₈ are each the same or different, hydrogen, a linear or branched aliphatic hydrocarbon having 1 to 6 carbon atoms, a cyanide group, a tertiary amine including an aliphatic hydrocarbon having 1 to 4 carbon atoms, and 1 to 4 carbon atoms aliphatic hydrocarbon, halogen, phenyl substituted with a cyanide group or an aldehyde group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms, halogen, pyridine substituted with a cyanide group or an aldehyde group.) 3. The method according to claim 2,
The urea-based solvent is a cured polymer stripper composition comprising the following formula (5):
[Formula 5]

(In Formula 5,
R ₉ and R ₁₀ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 6 carbon atoms, a phenyl group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms substituted with a methoxy group or a dimethylamino group.) 3. The method according to claim 2,
The cured polymer stripper composition, characterized in that the oxazolidinone-based solvent comprises the following formula (6):
[Formula 6]

(In Formula 6,
R ₁₁ is an aliphatic hydrocarbon having 1 to 6 carbon atoms, a phenyl group, or an aliphatic hydrocarbon having 1 to 4 carbon atoms substituted with a methoxy group or dimethylamino group.) 3. The method according to claim 2,
The phosphate-based solvent is a cured polymer stripper composition comprising the following Chemical Formula 7:
[Formula 7]

(In Formula 7,
R ₁₂ to R ₁₄ are the same or different, each of which is a phenyl group substituted with a linear or branched aliphatic hydrocarbon having 1 to 8 carbon atoms, an alkoxy group having 3 to 8 carbon atoms, a phenyl group, an aliphatic hydrocarbon having 1 to 4 carbon atoms, or halogen It is an aliphatic hydrocarbon having 2 to 4 carbon atoms.) According to claim 1,
The fluorine compound is
A cured polymer stripper composition comprising one selected from alkylammonium fluoride, alkylphosphonium fluoride, and alkylsulfonium fluoride. 11. The method of claim 10,
The alkylammonium fluoride is a cured polymer stripper composition comprising the following formula (8):
[Formula 8]

(In Formula 8,
m is an integer from 0 to 15,
n is an integer from 2 to 21.) 11. The method of claim 10,
The alkylphosphonium fluoride is a cured polymer stripper composition comprising the following formula (15):
[Formula 15]

(In Formula 15,
R ₁₅ to R ₁₈ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 22 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.) 11. The method of claim 10,
The cured polymer stripper composition, characterized in that the alkylsulfonium fluoride comprises the following formula (16):
[Formula 16]

(In Formula 16,
R ₁₉ to R ₂₁ are the same or different, respectively, an aliphatic hydrocarbon having 1 to 22 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.) According to claim 1,
The cation stabilizer is
12-Crown 4-Ether, 15-Crown 5-Ether, 18-Crown 6-Ether, 24-Crown 8-Ether, Benzo-12-crown 4-Ether, Benzo-15-crown 5-Ether, Dibenzo-15- A cured polymer stripper composition comprising one selected from crown 5-Ether and Dibenzo-18-crown 6-Ether.