TWI627251B - Composition, solution and membrane material for temporary bonding - Google Patents

Abstract

The present invention provides a composition for temporary bonding, a solution for temporary bonding, and a film for temporary bonding. The temporary adhesive composition includes a polyimide monomer, a flexible diamine having 36 carbon atoms, a light-absorbing dye, a solvent, and an epoxy resin.

Description

Composition for temporary bonding, solution for temporary bonding, and film for temporary bonding

The present invention relates to a temporary bonding composition, a temporary bonding solution, and a temporary bonding film, and more particularly, to a temporary bonding composition having good heat resistance and chemical resistance. Next, a solution and a temporary bonding film are used.

With the development of the microelectronics industry and the drive of the electronics market, semiconductor packaging technology is increasingly moving toward smaller, thinner, and better performance trends. In order to enable the wafer to better dissipate heat during use, extend the life and facilitate the subsequent system packaging, it is usually necessary to reduce the thickness of the wafer to 100 μm. Generally speaking, the wafer device is temporarily adhered to a thicker carrier glass first, and the wafer back is etched and polished to reduce a certain thickness, and then external light, electricity, heat or force is used to The adhesive layer fails, and the wafer device is separated from the carrier to complete. The temporary bonding layer used for the first release is critical for the successful implementation of the process. In more detail, the temporary bonding layer plays a very important role in the case where the wafer is temporarily fixed, the thick wafer is thinned and cut temporarily, and the transportation is temporarily fixed.

In the conventional technique, the debonding method of the temporary adhesive layer includes debonding by UV light irradiation, solvent debonding, or laser debonding. The heat-resistant temperature for debonding by UV light irradiation is about 120 ° C, which is easily affected by sun damage, causing the debonding reaction to occur early. The material suitable for debonding by UV light irradiation is silicone molecules or heat-resistant silicone resins, which are not synthesized Small molecules are easy to migrate, which may cause doubts about wafer line contamination. The disadvantage of solvent debonding is that the solvent resistance is poor, and chemical solvents are often used in general wet processes. Therefore, it may cause process limitations and thus do not meet market requirements.

Based on the above, the development of a temporary adhesive layer that reduces the adhesive force by laser absorption to improve the heat resistance and chemical resistance is an important subject for current research.

The invention provides a temporary adhesive composition, which loses adhesion under laser light with a wavelength of 355 nm or 532 nm, has good heat resistance and chemical resistance, and has a heat resistance temperature greater than 260 ° C (range 260 ° C to 399 ° C). ).

The temporary adhesive composition of the present invention includes a polyfluorene imine monomer, a flexible diamine having 36 carbon atoms, a light-absorbing dye, a solvent, and an epoxy resin.

In one embodiment of the present invention, the polyfluorene imide monomer includes a DABZ acid group and an OPDA.

In one embodiment of the present invention, the solvent includes cyclohexanone or toluene.

In one embodiment of the present invention, the light-absorbing dye includes a carbonyl dye, an azo dye, a sulfur dye, or a metal complex dye.

In one embodiment of the present invention, the metal complex dye contains chromium.

In one embodiment of the present invention, the epoxy resin includes a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cresol novolac epoxy resin, or a phenol novolac epoxy resin.

In an embodiment of the present invention, the soft diamine includes the following chemical structural formula: .

In an embodiment of the present invention, based on the total weight of the temporary subsequent composition, the amount of polyimide monomer is 10 wt% to 40 wt%, and the amount of soft diamine is 20 wt. % To 60 wt%, the light absorbing dye is added in an amount of 5 to 40 wt%, the solvent is added in an amount of 50 to 90 wt%, and the epoxy resin is added in an amount of 5 to 10 wt%.

The present invention provides a temporary bonding solution, including the above-mentioned temporary bonding composition, and can be applied by a spin coating method.

In one embodiment of the present invention, the temporary adhesive composition is diluted with a solvent to prepare a temporary adhesive solution, and the dilution ratio is 5% to 30%.

The present invention provides a temporary adhesive film including a substrate, a temporary adhesive layer formed of the temporary adhesive composition, and a protective layer, wherein the temporary adhesive layer is disposed on the substrate and the protective layer is disposed temporarily. Then layer up.

In one embodiment of the present invention, the thickness of the temporary adhesive layer is 0.5 μm to 10 μm.

Based on the above, the composition for temporary bonding of the present invention contains a polyfluoreneimide monomer and a flexible diamine, and therefore has good heat resistance and adhesion. In addition, due to the addition of light-absorbing dyes to increase the wavelength absorbance, the adhesive force can be lost under the irradiation of laser light with a wavelength of 355 nm or 532 nm. On the other hand, after the temporary bonding composition of the present invention is irradiated with laser light, the resin and the light absorbing dye are dispersed to be debonded, so there is no conventional problem of remaining the temporary bonding layer, and isopropyl alcohol can be used. It can be easily wiped and removed without plasma treatment, thereby improving the convenience of the process.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

In this article, a range represented by "one value to another value" is a summary representation that avoids enumerating all the values in the range one by one in the specification. Therefore, the record of a specific numerical range covers any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were explicitly written in the description. Same scope.

The invention provides a composition for temporary bonding, which can be used for preparing a solution for temporary bonding and a film for temporary bonding, and has the advantages of good heat resistance, good chemical resistance and low hygroscopicity. In the following, the embodiments are cited as examples in which the present invention can be surely implemented. ＜ Composition for temporary use ＞

The composition for temporary adhesion of the present invention includes a polyimide monomer, a flexible diamine, a light-absorbing dye, a solvent, and an epoxy resin, and has a solid content of, for example, 30% to 40%. Hereinafter, the above-mentioned various components will be described in detail. ＜ Polyimide monomer ＞

In this embodiment, the polyfluorene imide monomer may include a DABZ acid group and an OPDA, which may be represented by the following chemical structural formula: . The amount of the polyfluorene imide monomer to be added is, for example, 10 wt% to 40 wt% based on the total weight of the temporary subsequent use composition. The addition of polyimide monomer can improve the heat resistance of the subsequent composition and subsequent solutions and films. The heat resistance temperature is, for example, greater than 260 ° C, and more specifically, it can be heat resistant to 399 ° C. Therefore, It can improve the problem of poor heat resistance in conventional UV light debonding technology. ＜ flexible diamines ＞

In this embodiment, the carbon number of the flexible diamine is, for example, 36. The structure has no benzene ring and has good hydrophobicity, which can reduce the brittleness of the polyfluorene imine monomer. The amount of the flexible diamine to be added is, for example, 20 wt% to 60 wt% based on the total weight of the temporary subsequent composition. The soft diamine can include the following chemical structural formula: . ＜ Light-absorbing dyes ＞

In this embodiment, the light-absorbing dye may include a carbonyl dye, an azo dye, a sulfur dye, or a metal complex dye. More specifically, the metal complex dye may contain chromium. The light-absorbing dye is added in an amount of, for example, 5 wt% to 40 wt% based on the total weight of the temporary subsequent composition. The light-absorbing dye may include the following chemical structural formula: .

Due to the addition of light-absorbing dyes to increase the wavelength absorbance, the laser can cause carbonization and loss of adhesion under laser light with a wavelength of 355 nm or 532 nm. Compared with the conventional laser debonding technology, only The invention has the advantage of debonding under the irradiation of laser light with a wavelength of 355 nm. On the other hand, after the temporary bonding composition of the present invention is irradiated with laser light, the resin and the light absorbing dye are dispersed to be debonded, so there is no conventional problem of remaining the temporary bonding layer, and isopropyl alcohol can be used. It can be easily wiped and removed without plasma treatment, thereby improving the convenience of the process. < Solvent >

In this embodiment, the solvent may include cyclohexanone or toluene. The amount of the solvent to be added is, for example, 50 wt% to 90 wt% based on the total weight of the temporary subsequent composition. ＜ Epoxy resin ＞

In this embodiment, the epoxy resin may include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cresol novolac epoxy resin, or a phenol novolac epoxy resin. The amount of the epoxy resin to be added is, for example, 5 wt% to 10 wt% based on the total weight of the temporary subsequent composition. The epoxy resin may include the following chemical structural formulas: . < Temporary adhesive solution >

The temporary bonding solution of the present invention includes the above-mentioned temporary bonding composition and a solvent, and can be applied by a spin coating method. In this embodiment, the solvent may include cyclohexanone or toluene. The above-mentioned temporary adhesive composition is diluted with the solvent to prepare a temporary adhesive solution. The dilution ratio is, for example, 5% to 30%. The content is, for example, 7% to 14%. ＜ Film for temporary adhesion ＞

The present invention provides a film for temporary bonding. FIG. 1 is a schematic diagram of a temporary bonding film according to an embodiment of the present invention, in which each layer is not drawn according to an actual scale. Hereinafter, the temporary film material for the present invention will be described in detail with reference to FIG. 1.

As shown in FIG. 1, the temporary adhesive film 1000 of the present invention includes a substrate 100, a temporary adhesive layer 102, and a protective layer 104. The temporary adhesive layer 102 is disposed on the substrate 100 and the protective layer 104 is disposed on a temporary basis. Sex is on layer 102.

In this embodiment, the temporary bonding layer 102 is formed of the above-mentioned temporary bonding composition, and has a thickness of, for example, 0.5 μm to 10 μm and a warpage of less than 20 mm. The method for forming the temporary adhesive layer 102 is, for example, applying the above-mentioned temporary adhesive solution to the substrate 100, and then baking it at a temperature of 100 ° C to 140 ° C for 2 minutes to form it. At this time, the solvent is not contained in the temporary adhesive layer 102, and the solid content is, for example, 100%. The material of the substrate 100 may include a PET polyester film with a thickness of, for example, 75 μm to 100 μm. The material of the protective layer 104 may include a PET polyester film with a thickness of, for example, 25 μm to 50 μm.

Because the present invention has the advantage of low hygroscopicity, compared to the conventional product, it can only be applied to circular samples by spin coating in the form of a liquid coating. The temporary adhesive of the present invention can be pasted with a film. On square or irregularly shaped samples, it can better meet the needs of future square substrates.

On the other hand, the film for temporary bonding of the present invention can be debonded under irradiation of, for example, a laser power of 1 W to 4 W. After temporarily transferring the film material to the glass sample of the present invention, the film material may be directly irradiated with laser light for debonding, or the glass surface may be irradiated with laser light for debonding.

In the following, experimental examples will be used to explain in detail the temporary bonding composition and the produced film in the above-mentioned examples. However, the following experimental examples are not intended to limit the present invention. Experimental example

In order to prove that the temporary adhesive composition and the produced film material of the present invention have good heat resistance and chemical resistance and low hygroscopicity, this experimental example will be specifically described below. Thermal cracking temperature

Using a thermogravimetric analyzer (TGA), the temperature range is 0 to 600 ° C, and the heating rate is 20 ° C / min (° C / min). The temperature at% by weight is used as the thermal cracking temperature. The measured thermal cracking temperature is 399 ° C, which meets the requirement of greater than 300 ° C. Moisture absorption test

The temporary adhesive film (thickness: 20 μm) of the present invention is used as Example 1 and a commercially available product as a comparative example (for example, temporary adhesive glue of model OFPR-800LB produced by Tokyo Yinghua Industrial Co., Ltd.). In water, measure its moisture absorption rate. The measurement method of the moisture absorption rate test is as follows: Take a 5 * 5 temporary and then soak the membrane material in 100 ml of water for 12 hours, 24 hours, and 36 hours, and then measure their weight to obtain the moisture absorption rate. . The measurement results are shown in Table 1 below. In the film material of the present invention, after 36 hours of immersion, the moisture absorption rate is still less than 0.3%, while the commercial product as a comparative example has a moisture absorption rate of 4 after 12 hours of immersion Therefore, it can be known that the film material of the present invention has a low moisture absorption rate, and can be pasted on square or irregularly shaped samples, so it can better meet the needs of future square substrates. Table 1 <TABLE border = "1" borderColor = "# 000000" width = "85%"><TBODY><tr><td></td><td> Moisture absorption rate </ td></tr><tr><td> Example 1 </ td><td> Not soaked </ td><td> 0% </ td></tr><tr><td> Soaked for 12 hours </ td><td> 0.15 % </ td></tr><tr><td> Soak for 24 hours </ td><td> 0.20% </ td></tr><tr><td> Soak for 36 hours </ td><td> 0.26% </ td></tr><tr><td> Comparative example immersion for 12 hours </ td><td> 4% </ td></tr></TBODY></TABLE> Chemical resistance test

The temporary adhesive film of the present invention (the thickness of the temporary adhesive layer is 2 μm) is immersed in the different chemicals listed in Table 2 below for 10 minutes, and then measured by a tension meter. When the measurement result is higher than 550 When g / cm, it has good chemical resistance. The measurement results are shown in Table 2 below. It can be seen that the temporary film of the present invention exhibits good chemical resistance after being immersed in various chemical agents, even when immersed in PGMEA which is often used for solvent debonding Afterwards, it still has high chemical resistance. Therefore, the film material of the present invention can overcome the process limitation caused by poor solvent resistance in the conventional technology and closer to the market demand. Table 2 <TABLE border = "1" borderColor = "# 000000" width = "85%"><TBODY><tr><td><b> Chemicals </ b></td><td><b> Measurement results </ b><b> (g / cm) </ b></td></tr><tr><td> 100% NMP </ td><td> 585 </ td></td>tr><tr><td> 30% HCl </ td><td> 581 </ td></tr><tr><td> 10% NaOH </ td><td> 582 </ td></tr><tr><td> 100% PGMEA </ td><td> 574 </ td></tr><tr><td> 100% methanol </ td><td> 580 </ td></tr><tr><td> 100% acetone </ td><td> 572 </ td></tr></TBODY></TABLE>

In summary, since the composition for temporary bonding of the present invention contains a polyfluorene imine monomer and a flexible diamine, it has good heat resistance and adhesion. At the same time, the glass transfer temperature is adjusted to increase the transfer effect of the subsequently-made film materials, and the solvent resistance is improved by increasing the crosslinking degree. In this way, the problem of poor heat resistance and solvent resistance of the conventional UV light debonding and solvent debonding technologies can be solved, so as to overcome the process limitation and closer to the market demand. In addition, since the temporary bonding composition of the present invention does not contain silicon, it does not cause contamination of the wafer line.

On the other hand, due to the addition of light-absorbing dyes to increase the wavelength absorbance, the adhesive force can be lost under the irradiation of laser light with a wavelength of 355 nm or 532 nm. Compared with the conventional laser debonding technology, only The invention has the advantage of debonding under the irradiation of laser light with a wavelength of 355 nm. On the other hand, after the temporary bonding composition of the present invention is irradiated with laser light, the resin and the light absorbing dye are dispersed to be debonded, so there is no conventional problem of remaining the temporary bonding layer, and isopropyl alcohol can be used. It can be easily wiped and removed without plasma treatment, thereby improving the convenience of the process.

Compared with the conventional products, which can only be applied to circular samples by means of spin coating in the form of a liquid coating, the temporary adhesive film of the present invention has the advantage of low hygroscopicity, and can be pasted on squares or irregularly. The shape of the sample, so it can better meet the needs of future square substrates.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

100‧‧‧ substrate

102‧‧‧Temporary Bonding

104‧‧‧protective layer

1000‧‧‧ temporary adhesive film

FIG. 1 is a schematic diagram of a temporary bonding film according to an embodiment of the present invention.

Claims (12)

A temporary adhesive composition includes: a polyimide monomer; and a flexible diamine, wherein the carbon number of the flexible diamine is 36, and the structure of the flexible diamine is free of benzene. A ring; a light-absorbing dye; a solvent; and an epoxy resin, wherein the polyimide monomer is added in an amount of 10% to 40% by weight based on the total weight of the temporary subsequent composition, and the flexibility is The polyamine is added in an amount of 20 to 60 wt%, the light absorbing dye is added in an amount of 5 to 40 wt%, the solvent is added in an amount of 50 to 90 wt%, and the epoxy resin is added in an amount of 5 wt% To 10wt%. The temporary bonding composition according to item 1 of the scope of the patent application, wherein the light-absorbing dye includes a carbonyl dye, an azo dye, a sulfur dye, or a metal complex dye. The temporary bonding composition according to item 2 of the patent application scope, wherein the metal complex dye contains chromium. The temporary bonding composition according to item 1 of the scope of patent application, wherein the polyfluorene imine monomer includes a DABZ acid group and an OPDA. The temporary composition according to item 1 of the scope of application, wherein the solvent includes cyclohexanone or toluene. The temporary adhesive composition according to item 1 of the scope of the patent application, wherein the epoxy resin includes a bisphenol A epoxy resin, a bisphenol F epoxy resin, a cresol novolac epoxy resin, or a phenol novolac Type epoxy resin. The temporary bonding composition according to item 1 of the scope of the patent application, wherein the temporary bonding composition loses adhesion under the irradiation of laser light having a wavelength of 355 nm or 532 nm. The temporary bonding composition according to item 1 of the scope of application, wherein the heat-resistant temperature of the temporary bonding composition is from 260 ° C to 399 ° C. A temporary bonding solution includes the temporary bonding composition according to any one of claims 1 to 8 of the scope of patent application. The temporary bonding solution according to item 9 of the scope of the patent application, wherein the temporary bonding composition is diluted with a solvent to prepare the temporary bonding solution, and the dilution ratio is 5% to 30%. A temporary adhesive film material includes: a substrate; a temporary adhesive layer disposed on the substrate, and the temporary adhesive layer is composed of any one of items 1 to 8 of the scope of patent application. The temporary adhesion layer described above is formed with a composition; and a protective layer is disposed on the temporary adhesion layer. The film for temporary bonding according to item 11 of the scope of patent application, wherein the thickness of the temporary bonding layer is 0.5 μm to 10 μm.