TWI572490B - A stripping liquid composition, and a method of removing the polymer film using the release liquid composition - Google Patents

Description

Stripping liquid composition and method for removing polymer film using the stripping liquid composition

The present invention relates to a stripping liquid composition, and more particularly to a stripping liquid composition suitable for stripping a laser-treated polymer film.

The chip packaging technology has undergone changes, as the ratio of wafer area to package area is getting closer, the applicable frequency is increased, the heat resistance is improved, the number of wires is increased, the wire pitch is reduced, the weight is reduced, the reliability is improved, and the lead-free process is developed. It is known that the method of connecting a wafer and a printed substrate by wire bonding or the like has a problem that the number of wires is limited, the wiring between the wafers is long, the input/output buffer, the data transmission speed is difficult to be improved, and the high driving capability is required. The practice of enabling 2D to configure various ICs has gradually been replaced by three-dimensional chip (3D IC) packaging technology.

The 3D IC can connect multiple wafers with the shortest distance through the Through-Silicon Via (TSV) packaging technology, which not only shortens the wiring length between the wafers, but also increases the data transmission speed and reduces the power consumption. In addition, compared with the conventional printed circuit board, it is possible to increase the density of the wiring by using the yoke plate which is processed by the semiconductor technology. Therefore, a ruthenium adapter plate using a ruthenium material is currently used as a substrate on which an IC is mounted.

In the process of wafer thinning, the process of crystal back grinding (Grinding) is carried out. At the time of the wafer thickness reduction, the wafer strength is insufficient, which may cause the wafer to be easily cracked due to curl during the process of the process. Therefore, before the wafer is thinned, the wafer is usually loaded on a glass carrier with a polymer film (eg, epoxy resin) in a temporary bonding manner, and then continues. Process.

Moreover, since the thinned wafer must be de-bonded from the glass carrier plate at the end of the process, the polymer film is usually treated by laser to expand the treated polymer film so that the processed polymer film is expanded. A fine seam is formed between the wafer and the glass carrier plate to allow air to enter and peel off. Usually, after the polymer film is peeled off by the laser, the glass carrier sheet is likely to have a polymer film which is not completely peeled off, and must be completely cleaned before being recycled.

Currently, in the packaging process, the stripping solution for removing the polymer film is usually composed of an organic base and a polar solvent. However, the stripping solution removes the laser-treated polymer film on the glass, which is not effective, and easily causes the polymer film to remain. Or, although the polymer film can be removed, the glass carrier plate is also damaged, so that the glass carrier plate cannot be reused, resulting in cost waste.

Therefore, at present, the industry still needs to develop a stripping liquid composition which can effectively peel off the polymer film without damaging the glass carrier sheet.

The present invention provides a stripping liquid composition comprising: an inorganic base, the inorganic base content is 5 to 25% based on the total weight of the stripping liquid composition; and an amine compound, based on the total weight of the stripping liquid composition The content of the amine compound is 5 to 30%; the polar solvent is 5 to 60% by weight based on the total weight of the stripping liquid composition; and an aqueous medium.

In order to achieve a good peeling effect of the stripping liquid composition of the present invention, the present invention provides a method for removing a polymer film, comprising: removing a polymer film formed on a carrier sheet by the above-described stripping liquid composition.

In the method of the present invention, the polymer film is removed at a temperature of 50 to 90 ° C in the stripper composition. In a preferred embodiment, the polymeric film is removed at a temperature of from 60 to 70 °C.

In the method of the present invention, the polymer film is an epoxy resin film. In a preferred embodiment, the polymeric film is a laser treated epoxy film.

In the method of the present invention, the polymer film formed on the carrier sheet is removed by rinsing or immersion.

In the above method, the carrier film can be brushed by a brush to remove the polymer film formed on the carrier plate, whether the polymer film formed on the carrier plate is removed by rinsing or immersion.

In the peeling liquid composition of the present invention and the method for removing the polymer film, the inorganic base is at least one selected from the group consisting of alkali metal hydroxides. In a preferred embodiment, the alkali metal hydroxide is selected from at least one of the group consisting of sodium hydroxide and potassium hydroxide.

In the stripping liquid composition and the stripping method of the present invention, the polar solvent is selected from the group consisting of Dimethyl sulfoxide, Diethylene glycol monobutyl ether, Benzyl alcohol, and N. , N-Dimethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone, γ-butyl In the group consisting of gamma-butyrolacton and N,N-dimethylimidazol At least one.

In the peeling liquid composition and the peeling method of the present invention, the amine compound is at least one selected from the group consisting of an alkanolamine and an alkylamine. In a preferred embodiment, the amine compound is selected from the group consisting of Monoethanolamine, Monoisopropanolamine, Triethanolamine, N-Methyldiethanolamine, and Isobutanolamine. (Isobutanolamine) at least one of the group consisting of.

In the stripping liquid composition and the stripping method of the present invention, the aqueous medium is deionized water or pure water.

Further, in the stripping liquid composition and the peeling method of the present invention, a surfactant is further included, and the content of the surfactant is 0.01 to 1% based on the total weight of the stripping liquid composition. In a preferred embodiment, the surfactant is selected from at least one of the group consisting of a nonionic surfactant and an anionic surfactant.

The stripping liquid composition of the present invention achieves a good effect of removing the polymer film by micro-etching the polymer film on the surface of the carrier plate by the inorganic base without slightly damaging the carrier plate. Further, as described above, since the stripping liquid composition of the present invention is supplemented with an inorganic base by an amine compound, the effect of removing the polymer film is achieved. Therefore, the stripping liquid composition of the present invention can achieve the effect of not damaging the carrier sheet without adding or containing an organic base, that is, in the case of effectively removing the polymer film.

The embodiments of the present invention are further described by the specific embodiments thereof, and those skilled in the art can understand the other advantages and effects of the present invention from the disclosure of the present disclosure. The embodiment of the present invention is shown below, but the present invention is not limited to these embodiments. In addition, the term "microetching" as used herein means that, although the surface is etched, only the surface area of the carrier plate is less than 1%, and the surface of the carrier plate is corroded to cause pockets, notches or depressions. damage. The amine compound described in the present invention means a primary, secondary or tertiary amine compound, but does not include a quaternary ammonium salt compound.

The stripping liquid composition of the present invention comprises 5 to 25% of an inorganic base, 5 to 30% of an amine compound, 5 to 60% of a polar solvent, and deionized water based on the total weight of the stripping liquid composition.

In the composition of the stripping liquid of the present invention, the polymer film is dissolved by a polar solvent to achieve the effect of removing the polymer film. In the present invention, the selection of the polar solvent is not particularly limited, and it is generally a commonly used polar solvent, and will not be described herein.

In the stripping liquid composition of the present invention, the surface of the glass is microetched by an inorganic base to achieve the effect of peeling off the polymer film. In the present invention, the inorganic base is an alkali metal hydroxide. In the following examples, sodium hydroxide and potassium hydroxide were exemplified, and the polymer film was peeled off from the alkali metal hydroxide.

In the stripping liquid composition of the present invention, the amine compound is at least one selected from the group consisting of an alkanolamine or an alkylamine.

In a preferred embodiment, the amine compound is selected from the group consisting of primary, secondary, and And at least one of the group consisting of tertiary amine compounds.

In one embodiment, the amine compound is a tertiary amine compound, wherein the number of -OH groups in the amine compound is 3 or less, preferably selected from the group consisting of triethanolamine and N-A. At least one of the group consisting of N-Methyldiethanolamine.

In one embodiment, the amine compound is monoethanolamine, and the monoethanolamine is present in an amount of from 10% to 20% based on the total weight of the stripper composition.

In the stripping liquid composition of the present invention, the amine compound is used to assist the inorganic base to peel off the polymer film, and the service life of the stripping liquid composition can be prolonged.

The method of the present invention removes the polymer film formed on the carrier sheet using the stripping liquid composition of the present invention. In the method of the present invention, the manner of removing the polymer film is not particularly limited, and the polymer film may be peeled off by immersion or rinsing.

Example Example 1 Preparation of the stripping liquid composition of the present invention

The peeling liquid composition of the first embodiment of the present invention is obtained by dissolving 5 parts by weight of sodium hydroxide, 5 parts by weight of isobutanolamine, and 60 parts by weight of diethylene glycol monobutyl ether in deionized water. The content of the sodium hydroxide was 5%, the content of isobutanolamine was 5%, and the content of diethylene glycol monobutyl ether was 60% based on the total weight of the stripping liquid composition.

Examples 2 to 18 Preparation of the stripping liquid composition of the present invention

The procedure of Example 1 was repeated, but using the components shown in Table 1, The stripping liquid compositions of Examples 2 to 18 were prepared in accordance with the amounts shown in Table 2.

Comparative Example 1 Using only an inorganic base as a stripping solution

Dissolving 45 wt% of potassium hydroxide in deionized water to prepare a comparative example 1 stripping solution.

Comparative Example 2 Conventional stripping liquid composition

1 part by weight of 1% tetramethylammonium hydroxide (TMAH) and 96 parts by weight of dimethyl sulfoxide (DMSO) were dissolved in deionized water to prepare a stripping solution of Comparative Example 2. Things.

Comparative Example 3 Using only an inorganic base as a stripping solution

2 parts by weight of 2% tetramethylammonium hydroxide (TMAH) and 92 parts by weight of dimethyl sulfoxide (DMSO) were dissolved in deionized water to prepare a stripping solution of Comparative Example 3. Things.

Test method The method for removing the polymer film of the present invention

An epoxy resin film is formed on the glass carrier plate, and the epoxy resin film is irradiated with laser light to obtain a glass carrier plate having a laser-treated epoxy resin film.

The temperatures of the stripping liquid compositions of Examples 1 to 18 and Comparative Examples 1 to 3 were adjusted according to Tables 2 and 3, and the stripping liquid compositions of Examples 1 to 18 and Comparative Examples 1 to 3 were respectively sprayed (Spray). The brush was assisted by a brush for 1 minute to remove the laser-treated epoxy film obtained by the aforementioned method.

X-ray photoelectron spectroscopy/Electron Spectroscopy for Chemical Analysis (XPS/ESCA) was performed using an X-ray photoelectron spectrometer (Model K-Alpha) from Thermo Scientific, and the stripping by the present invention was measured. After the liquid composition was removed from the epoxy resin, the amount of carbon remaining on the glass carrier plate was determined based on the total surface area of the glass carrier plate to confirm whether or not epoxy resin remained, and the results are reported in Tables 2 and 3.

And visually observe whether the appearance of the glass carrier plate changes. The evaluation was carried out as follows, and the results were recorded in Table 2 and Table 3: ◎: good, the appearance of the carrier plate was good, and the surface was completely free of corrosion, such as pockets, notches or depressions; ○: good, The total surface area of the carrier plate is less than 1% of the surface of the carrier plate is corroded to cause damage such as pockets, notches or depressions; △: Yes, based on the total surface area of the carrier plate, 1 to 10% of the surface of the carrier plate is Corrosion causes damage such as pockets, notches or sags; and ×: Poor, based on the total surface area of the carrier plate, more than 10% of the surface of the carrier plate is corroded to cause damage such as pockets, notches or sags.

As shown in Tables 2 and 3, Comparative Example 1 using only an inorganic base as a stripping solution not only failed to effectively remove the epoxy resin, but also excessively corroded the glass bearing. The plate causes the glass carrier plate to cause damage such as pockets, notches or depressions. Further, the peeling liquid compositions of Comparative Examples 2 and 3 did not damage the carrier sheet, but could not effectively remove the epoxy resin. In view of Comparative Examples 1 to 3, the peeling liquid compositions of Examples 1 to 18 of the present invention not only have a good epoxy resin removing effect, but also do not damage the carrier sheet.

As shown in the results of Tables 2 and 3, the peeling liquid compositions of Examples 1 to 18 of the present invention were used for peeling as compared with Comparative Examples 1 to 3, and the thunder was effectively removed without damaging the glass carrier plate. A treated epoxy film.

In summary, the stripping liquid composition of the present invention can effectively control the removal of the polymer film without adding an organic base, and the absence of appearance corrosion does not occur on the carrier sheet.

The above-described embodiments are merely illustrative of the principles of the invention and its effects, and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the present invention should be as set forth in the scope of the claims, and the technical contents disclosed in the present invention should still be obtained without affecting the effects and the objects that can be achieved by the present invention. Can cover the scope.

Claims (20)

A stripping liquid composition for stripping a laser-treated polymer film, comprising: an inorganic base, the inorganic base content is 5 to 25% based on the total weight of the stripping liquid composition; an amine compound, The amine compound is contained in an amount of 5 to 30% by weight based on the total weight of the stripping liquid composition; and the polar solvent is contained in an amount of 5 to 60% by weight based on the total weight of the stripping liquid composition; medium. The peeling liquid composition according to claim 1, wherein the inorganic base is contained in an amount of 10 to 20% based on the total weight of the stripping liquid composition. The peeling liquid composition according to claim 1, wherein the amine compound is contained in an amount of 5 to 20% by weight based on the total weight of the stripping liquid composition. The peeling liquid composition according to claim 1, wherein the polar solvent is contained in an amount of 10 to 30% based on the total weight of the stripping liquid composition. The peeling liquid composition according to claim 1, wherein the inorganic base is at least one selected from the group consisting of alkali metal hydroxides. The stripping liquid composition according to claim 5, wherein the alkali metal hydroxide is selected from the group consisting of sodium hydroxide and potassium hydroxide. At least one of the groups. The stripping liquid composition according to claim 1, wherein the polar solvent is selected from the group consisting of Dimethyl sulfoxide, Diethylene glycol monobutyl ether, and Benzyl (Benzyl). Alcohol), N,N-Dimethylacetamide, N,N-Dimethylformamide, and N-Methyl-2-Pyrrolidone And at least one of a group consisting of gamma-butyrolacton and N,N-dimethylimidazol. The peeling liquid composition according to claim 1, wherein the amine compound is at least one selected from the group consisting of an alkanolamine and an alkylamine. The peeling liquid composition according to claim 8, wherein the amine compound is selected from the group consisting of Monoethanolamine, Monoisopropanolamine, Triethanolamine, and N-methyldiethanolamine. (N-Methyldiethanolamine) and at least one of the group consisting of Isobutanolamine. The peeling liquid composition according to claim 1, wherein the aqueous medium is deionized water or pure water. The stripping liquid composition according to claim 1, further comprising a surfactant, wherein the surfactant is contained in an amount of 0.01 to 1% by weight based on the total weight of the stripping liquid composition. The peeling liquid composition according to claim 11, wherein the surfactant is at least one selected from the group consisting of a nonionic surfactant and an anionic surfactant. A method for removing a laser-treated polymer film, comprising: removing a polymer film formed on a carrier sheet by using a stripping liquid composition as described in claim 1 of the patent application. The method of claim 13, wherein the carrier plate is a glass substrate. The method of claim 13, wherein the polymer film is an epoxy resin film. The method of claim 15, wherein the polymer film is a laser treated epoxy film. The method of claim 13, wherein the polymer film formed on the carrier sheet is removed by rinsing or immersion. The method of claim 17, further comprising brushing the carrier plate with a brush to remove the polymer film on the carrier plate. The method of claim 13, wherein the temperature of the stripping liquid composition is between 50 and 90 ° C, and the polymer film is removed under the temperature condition. The method according to claim 19, wherein the temperature of the stripping liquid composition is between 60 and 70 ° C, and the polymer film is removed under the temperature condition.