KR20160112401A - Composition for removing silicone polymer - Google Patents
Composition for removing silicone polymer Download PDFInfo
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- KR20160112401A KR20160112401A KR1020150038090A KR20150038090A KR20160112401A KR 20160112401 A KR20160112401 A KR 20160112401A KR 1020150038090 A KR1020150038090 A KR 1020150038090A KR 20150038090 A KR20150038090 A KR 20150038090A KR 20160112401 A KR20160112401 A KR 20160112401A
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- Prior art keywords
- fluoride
- composition
- silicone
- fluorine compound
- group
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
Abstract
The present invention relates to a silicone-based resin removing composition, and more particularly, to a composition for removing a silicone-based resin containing sulfuric acid or an organic sulfonic acid, a fluorine compound and water.
The composition for removing silicone resin is excellent in the decomposition rate of resin and has an effect of suppressing corrosion on SiN film or Poly-Si film to improve the process of manufacturing electronic parts and the like, such as back grinding of semiconductor wafer, The silicon-based resin remaining on the support and the wafer circuit surface can be effectively removed.
Description
The present invention relates to a silicone resin composition capable of securing an excellent silicone resin dissolution rate and a protective effect on a lower film.
BACKGROUND ART [0002] In an electronic device manufacturing process, an electronic circuit or the like is formed on the surface of a semiconductor wafer (hereinafter simply referred to as a " wafer ") and then subjected to back grinding (so-called back grinding) There is a case. In this case, for the purpose of protecting the wafer circuit surface and securing the wafer, a support body is usually attached to the circuit surface of the wafer via a silicone resin. When the support is attached to the circuit surface of the wafer, it is possible to reinforce the wafer having a reduced thickness after the back grinding of the wafer, and to form the back electrode or the like on the grinding surface of the wafer.
After the back grinding of the wafer and the formation of the back electrode are completed, the support is removed from the circuit surface of the wafer, the silicon resin attached to the electronic component is peeled and removed, and the wafer is cut to manufacture chips.
On the other hand, in recent years, a chip stacking technique using a penetrating electrode (for example, a silicon penetrating electrode) that penetrates a wafer has been developed. According to this chip stacking technique, since electronic circuits of a plurality of chips are electrically connected to each other by using a through electrode instead of a conventional wire, high integration of chips and high operation speed can be achieved. In the case of using this chip stacking technique, back grinding of the wafer is often performed in order to reduce the thickness of the aggregate in which a plurality of chips are stacked, thereby increasing the number of cases in which a silicon resin is used for a support or an electronic component.
Conventionally, after attaching a support to a circuit surface of a wafer via a silicone-based resin attached to an electronic component and then thermally curing the wafer and the support for firm attachment, the silicone resin adhered to the electronic component is peeled off , A silicone resin adhered to the cured electronic component may remain on the circuit surface of the support and the wafer. Therefore, a means for efficiently removing the silicon-based resin adhered to the support and the cured electronic component remaining on the wafer circuit surface is needed.
U.S. Patent No. 6,818,608 discloses a composition for dissolving a cured polymer resin composed of an organic fluoride, a soluble amine, and a solvent. In this case, the solvent used is methyl ethyl ketone and n, n-dimethylacetamide, and further includes a co-solvent of glycol ethers.
In this patent, although the above-mentioned composition is used to efficiently remove the cured silicone polymer, the effect is not sufficient in terms of the removal rate or stability, and the working environment is also poor due to the use of the organic solvent.
As a result of various studies in order to promote the silicon dissolution reaction and to secure a protective effect on other layers laminated together, the Applicant has found that when using sulfuric acid or organic sulfonic acid, fluorine compound and water, The present invention has been completed.
Accordingly, an object of the present invention is to provide a composition for removing a silicone resin, which has an excellent decomposition reaction rate in the removal of a silicone resin used for electronic parts and the like, and an anti-corrosion effect against other film quality.
In order to achieve the above object, the present invention provides a composition for removing a silicone resin comprising sulfuric acid or an organic sulfonic acid, a fluorine compound and water.
The organic sulfonic acid is represented by the following general formula (1).
[Chemical Formula 1]
(Wherein R 1 is as described in the specification)
The silicone resin-removing composition is characterized by containing 80 to 99.9% by weight of sulfuric acid or organic sulfonic acid, 0.05 to 7% by weight of a fluorine compound, and water as a balance so as to satisfy 100% by weight of the total composition.
The composition for removing a silicone resin according to the present invention is excellent in decomposition speed of a silicone resin and suppresses corrosion on SiN and Poly-Si films stacked together. Therefore, in the manufacturing process of electronic parts and the like, It is possible to effectively remove the support and the silicon-based resin remaining on the wafer circuit surface in a process such as formation.
The present invention discloses a silicone-based resin removing composition for selectively cleaning and cleaning a silicone resin adhered to an electronic component or the like.
The silicone-based resin has a plurality of Si-O bonds in the molecular structure, and the composition for cleaning the silicone-based resin includes a solvent for swelling the silicone-based resin and for dissolving the fluorine compound and a solvent for dissolving the Si- Fluorine compounds. As the solvent, an organic solvent is generally used. As the fluorine compound, an alkylammonium fluoride compound represented by tetra-butyl ammonium fluoride (TBAF) is used.
However, problems of aging change due to odor, volatilization and moisture absorption occurring in ketone solvents mainly used as organic solvents are caused, and the working environment is very poor. In addition, compositions with conventional compositions exhibit side effects that damage the support and other films deposited together on the wafer side.
Accordingly, the present invention makes it possible to carry out the above-described role more stably and effectively by using a composition for removing a silicone resin composed of sulfuric acid or organic sulfonic acid, a fluorine compound and water.
Specifically, the sulfuric acid or the organic sulfonic acid is excellent in solubility to the siloxane and oxidizes and dissolves the silicone resin. Further, the fluorine compound contains fluorine ions in the molecular structure and attacks the Si of the silicon-based resin by utilizing the fact that the bonding force of Si-F is stronger than the bonding force of Si-O, thereby performing the Si-O bond decomposition reaction. In addition, it is possible to improve the working environment with a composition containing only a small amount of water for dissolving the fluorine compound without using an organic solvent, and it has an advantage that the silicone resin having a high crosslink density has a sufficient decomposition ability.
Each composition will be described below.
The silicone-based resin removing composition of the present invention includes sulfuric acid or organic sulfonic acid. This is excellent in solubility in the siloxane constituting the silicone resin, and serves to decompose the silicone resin through the oxidation reaction with the silicone resin.
The sulfuric acid used in the present invention can be prepared directly as a compound represented by H 2 SO 4 or commercially available. Such sulfuric acid is generally used in the form of an aqueous solution which is generally dispersed in water. In particular, in order to use the composition for removing a silicone resin as in the present invention, it is preferably used in the form of an aqueous sulfuric acid solution.
The concentration of the aqueous sulfuric acid solution used in the present invention may be 50 to 99%, preferably 80 to 97%. However, the aqueous sulfuric acid solution can have various concentration ranges, which can be manufactured by hand or commercially available products.
The organic sulfonic acid in the present invention is a kind of an organic acid having a sulfonic acid group (-SO 3 H) and is characterized by being represented by the following formula (1).
(In the formula 1,
R 1 is an aryl group or a cycloalkyl group of C 6-20 alkyl group of C 1-25, C 3-25, wherein the aryl group within a cycle of at least one carbon atom of the alkyl group C 1-12, C 3-12 molecules Substituted or unsubstituted alkyl group)
The term " alkyl group " used in the present invention includes straight or branched alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n- butyl, isobutyl, pentyl, hexyl, Dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, and the like.
As used herein, a "cycloalkyl group" is a fully saturated and partially unsaturated hydrocarbon ring of carbon atoms, including cyclopropyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, adamantyl, and substituted and unsubstituted boronyl, Norbornyl, and norbornenyl.
The "aryl group" referred to in the present invention includes one or more rings having 6 or more atoms in a monocyclic or bicyclic aromatic ring and up to 5 rings containing up to 22 atoms may be present And there can be alternating double bonds between adjacent carbon atoms or suitable heteroatoms. Specific examples include phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl, pyrenyl and the like.
The term " unsubstituted " in the present invention means having no substituent other than hydrogen.
Preferably, R 1 is a C 1-12 alkyl group or a C 6-12 aryl group substituted with a C 1-12 alkyl group.
The organic sulfonic acid represented by the above formula (1) may be prepared directly or use a commercially available one, and any of those known in the art may be used. Examples thereof include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid (4-methylbenzenesulfonic acid), and dodecylbenzenesulfonic acid.
Such sulfuric acid or organic sulfonic acid may be used in an amount of 80 to 99.9% by weight, preferably 90 to 99.9% by weight, more preferably 95 to 99.9% by weight within 100% by weight of the total composition. When the sulfuric acid or the organic sulfonic acid is used in an amount of less than 80% by weight, the dissolution rate of the silicone-based resin is lowered. If the sulfuric acid or the organic sulfonic acid is used in an amount exceeding 99.9% by weight, decomposition of the silicone-
The fluorine compound in the present invention is a compound capable of dissociating into fluorine ion or polyatomic fluorine ion, and serves to decompose the silicone resin through the reaction of silicon.
The fluorine compound may be selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, alkylammonium fluoride, and combinations thereof.
The alkylammonium fluoride is specifically exemplified by tetra-methyl ammonium fluoride, tetra-ethyl ammonium fluoride, tetra-propyl ammonium fluoride, tetrabutylammonium tetra tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, diethyldimethylammonium fluoride, methyl tributylammonium fluoride, tetrabutylammonium fluoride, tetrabutylammonium fluoride, tetrabutylammonium fluoride, tetrabutylammonium fluoride, methyltributylammonium fluoride), and a combination thereof.
The fluorine compound of the present invention is preferably hydrofluoric acid or ammonium fluoride.
Such a fluorine compound is preferably used in an amount of 0.05 to 7% by weight, more preferably 0.1 to 5% by weight, in 100% by weight of the whole composition. When the amount of the fluorine compound is less than 0.05 wt%, the decomposition reaction of the silicone resin does not proceed. On the contrary, when the fluorine compound is used in an amount exceeding 7 wt%, the dissolution rate of the silicone resin is slowed and corrosion of other film materials such as SiN or Poly- Can occur.
The silicone-based resin removing composition of the present invention contains water because the above-mentioned fluorine compound is applied in an aqueous solution state. That is, water mainly aims to dissolve a fluorine compound, dissolves or disperses the above-mentioned composition, and further makes a silicon-based resin decomposition reaction more easily by fluorine ions.
In view of the application to the semiconductor process, which is a particularly suitable application for the present invention, the water is essentially required to be clean water. Specifically, it is preferable that the number of metals and other impurities that can affect the semiconductor is as small as possible. Examples of the method for obtaining such water include ion exchange method and the like.
The content of such water is not particularly limited, but may be included as a remainder to satisfy 100 wt% of the entire composition. The content of water in the present invention may be varied depending on the content of the fluorine compound mentioned above, and it is specifically used in a minimum content range capable of dissolving the fluorine compound used. In the composition of the present invention, when sulfuric acid is used, heat is generated when the content of water is increased, and damage to other films formed on the wafer or the wafer due to generated heat may occur.
In addition, the silicone-based resin removing composition according to the present invention may optionally contain at least one additive. Suitable additives include corrosion inhibitors, surfactants, wetting agents, cryoprotectants, viscosity modifiers, and the like, which are commonly used in the art. But is not limited to, preferably, a corrosion inhibitor or a surfactant.
The corrosion inhibitor is used to effectively inhibit the corrosion of the metal-containing lower film during resin removal, for example, catechol; (C 1-6 ) alkyl catechols, such as methyl catechol, ethyl catechol and tert-butyl catechol; Benzotriazole; Hydroxyanisole; (C 1-10 ) alkylbenzotriazole; Hydroxy (C 1-10 ) alkylbenzotriazole; 2-mercaptobenimidazole; Gallic acid; Gallic acid esters such as methyl gallate and propyl gallate; And tetra (C 1-4 ) alkylammonium silicates, such as tetramethylammonium silicate. Such corrosion inhibitors are generally commercially available from various sources, such as Aldrich Chemical Company (Milwaukee, Wisconsin) and may be used without further purification.
The surfactant may be used for enhancing cleaning properties. For example, anionic surfactants, cationic surfactants and nonionic surfactants can be used. Among them, nonionic surfactants having excellent wettability and less bubble formation are preferably used.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl 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. Can be mixed and used.
The silicone-based resin in the present invention is not particularly limited as long as it is a resin containing a siloxane bond in the resin. For example, the silicone-based resin means a polymer used for adhesion purposes produced by copolymerization of dimethylsiloxane. Specifically, , ≪ / RTI > M, D, T, Q,
The M unit refers to a so-called monofunctional siloxane unit which may be represented by the general formula [R 3 SiO 1/2 ], and the D unit is usually represented by the formula [R 2 SiO 2/2 ] Refers to a so-called bifunctional siloxane unit, and the T unit usually means a so-called trifunctional siloxane unit represented by the formula [RSiO 3/2 ], and the Q unit is usually represented by the formula [SiO 4/2 ] May be referred to as a " tetrafunctional siloxane unit " In the above, R is a substituent group directly bonded to a silicon atom. Examples of the substituent include hydrogen, a hydroxyl group, an epoxy group, an acryl group, a methacryl group, an acryloyl group, a methacryloyl group, an isocyanate group, A monovalent hydrocarbon group or the like.
For example, the silicone resin may be an adhesive. The silicone based adhesive is a system that can withstand the backgrinding process and the back electrode forming process sufficiently by bonding the semiconductor substrate to a supporting substrate such as silicon or glass through an adhesive. The important point here is the adhesive used when bonding both substrates. This adhesive should be able to easily peel the thin wafer from the support substrate at the end of the process as well as sufficient adhesion and durability. As described above, this adhesive is referred to as an adhesive because it is peeled off at the end.
Further, the present invention can remove the silicone resin used for adhering to electronic parts or the like by using the silicone-based resin removing composition. That is, the present invention removes the silicon-based resin remaining on the substrate or the wafer by spraying it onto the silicone-based resin removing composition or spraying it through a nozzle. The amount of the silicone-based resin-removing composition to be dripped or injected can be controlled depending on the kind of the silicone resin used and the thickness of the film.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, 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 5: Preparation of composition for removing silicone resin
A silicone-based resin removing composition was prepared according to the components and compositions shown in Table 1 below.
2) A-2: Hydrofluoric acid
Experimental Example 1: Performance Test
(1) Cleaning property evaluation for silicone resin
Silicone resin (Shin-Etsu KE-3417) was applied to the wafer by a spin coating method and then cured at 150 캜 for 20 minutes to form a silicone coating layer having a thickness of 80 탆. The specimens were cut to a size of 2 X 2 cm to prepare specimens for cleaning property evaluation.
The specimens were immersed at 60 DEG C for 5 minutes while stirring the composition prepared in the above Examples and Comparative Examples at 350 rpm.
Then, the specimen was taken out, washed with water and dried, and then the thickness of the cured silicone resin was measured with an SEM (S-4700; Hitachi).
The cleanability was evaluated by the following criteria.
<Standard>
?: 90%? Film removal rate
?: 80%? Film removal rate <90%
?: 50%? Film removal rate <80%
×: 50% <film removal rate
(2) Evaluation of damage to SiN film or Poly-Si film
SiN film and Poly-Si film were cut to a size of 2 X 2 cm to prepare specimens.
The specimens were immersed at 60 DEG C for 5 minutes while stirring the composition prepared in the above Examples and Comparative Examples at 350 rpm.
Subsequently, the specimens were taken out, washed with water and dried. Thereafter, the thicknesses of the SiN film and the poly-Si film were measured with an SEM (S-4700, Hitachi). The results are shown in Table 2 below.
(Å / min)
(Å / min)
Referring to Table 2, the cleaning properties of Examples 1 to 5 including sulfuric acid or organic sulfonic acid and fluorine compound were improved compared to the comparative examples, and it was confirmed that they have protective effects on other film materials such as SiN and Poly-Si Respectively.
Examples 1 to 3 show that as the content of the fluorine compound increases, the cleanability is good but the corrosion to the SiN and poly-Si film is increased. In the case of using only sulfuric acid or methanesulfonic acid as in Comparative Examples 1 and 2, no corrosion occurred in SiN and poly-Si, but the cleansing property against silicone resin was lower than those in Examples and Comparative Example 3 using sulfuric acid or an acid other than organic sulfonic acid To 5, it was confirmed that the silicone resin was not removed.
The composition for removing a silicone resin of the present invention has excellent silicone resin decomposition and excellent protective effect on other film quality, so that the remaining silicon resin is very effectively removed, so that the manufacturing process of electronic parts and the like, for example, the back grinding of a semiconductor wafer, . ≪ / RTI >
Claims (6)
[Chemical Formula 1]
(In the formula 1,
R 1 is an aryl group or a cycloalkyl group of C 6-20 alkyl group of C 1-25, C 3-25, wherein the aryl group within a cycle of at least one carbon atom of the alkyl group C 1-12, C 3-12 molecules Substituted or unsubstituted alkyl group)
From 80 to 99.9% by weight of sulfuric acid or organic sulfonic acid,
0.05 to 7% by weight of a fluorine compound and
Wherein the remainder comprises water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150038090A KR20160112401A (en) | 2015-03-19 | 2015-03-19 | Composition for removing silicone polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150038090A KR20160112401A (en) | 2015-03-19 | 2015-03-19 | Composition for removing silicone polymer |
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| KR20160112401A true KR20160112401A (en) | 2016-09-28 |
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| KR1020150038090A KR20160112401A (en) | 2015-03-19 | 2015-03-19 | Composition for removing silicone polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437883A (en) * | 2020-11-06 | 2022-05-06 | 凯斯科技股份有限公司 | Composition for dissolving polishing particles and cleaning method using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818608B2 (en) | 2002-02-01 | 2004-11-16 | John C. Moore | Cured polymers dissolving compositions |
-
2015
- 2015-03-19 KR KR1020150038090A patent/KR20160112401A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6818608B2 (en) | 2002-02-01 | 2004-11-16 | John C. Moore | Cured polymers dissolving compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437883A (en) * | 2020-11-06 | 2022-05-06 | 凯斯科技股份有限公司 | Composition for dissolving polishing particles and cleaning method using the same |
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