Composition for surface protection, surface protective sheet, and method for manufacturing electronic component device

Abstract

Provided is a composition for surface protection which protects at least one surface of a substrate, and contains: a polymer that has a hydrophilic group in a molecule; and a compound that generates an acid or a base by means of at least one of heating or active energy ray irradiation.

Description

Surface protection composition, surface protection sheet, and method for manufacturing electronic component device CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from Japanese Patent Application No. 2022-063386, which is incorporated herein by reference.

[0002] The present invention relates to a surface protective composition and a surface protective sheet used in the manufacture of electronic component devices such as semiconductor integrated circuits, etc. The present invention also relates to a method for manufacturing an electronic component device using the surface protective composition or the surface protective sheet.

[0003] Conventionally, there have been known manufacturing methods for electronic component devices, such as semiconductor integrated circuits. In this type of manufacturing method for electronic component devices, a substrate, such as a silicon wafer, is divided into small pieces to produce a large number of chips. During this process, when the substrate is divided into small pieces, a small portion of the substrate may become tiny pieces, resulting in minute foreign matter. When circuit components, such as circuit wiring or electrodes, are arranged on one side of the substrate, minute foreign matter may adhere to the circuit wiring or electrodes. Furthermore, foreign matter may also adhere to the other side, where circuit components, such as circuit wiring or electrodes, are not arranged. When a large amount of foreign matter adheres to the surface of the substrate, the reliability of the manufactured electronic component device may be reduced, regardless of whether circuit components are arranged on the side with the foreign matter attached.

[0004] In response to this, there is known a method of manufacturing an electronic component device in which a protective adhesive tape is attached to at least one surface of the substrate before the above-described processing is carried out (for example, see Patent Document 1).

[0005] The method for manufacturing an electronic component device described in Patent Document 1 uses a semiconductor protective adhesive tape having a substrate and a photocurable adhesive layer (protective layer) superimposed on one side of the substrate. The substrate has a specific thickness and is designed to have a specific heat shrinkage rate after heating at 150°C for 30 minutes. The photocurable adhesive layer (protective layer) is formed from a composition with a predetermined formulation, has a predetermined thickness, and is designed to have a relatively small predetermined adhesive strength after light irradiation. More specifically, the method for manufacturing an electronic component device described in Patent Document 1 first superimposes the photocurable adhesive layer (protective layer) of the protective adhesive tape on the circuit surface of a substrate (hereinafter referred to as a semiconductor package) on which a circuit is formed, and then divides the protective adhesive tape and the semiconductor package in this superimposed state into small pieces. Next, the small semiconductor packages and the protective adhesive tape are attached to the temporary fixing tape so that the circuit surface of the small semiconductor packages faces the temporary fixing tape and so that the temporary fixing tape contacts the substrate of the protective adhesive tape. Next, a metal film is formed on a part of the surface of the semiconductor package in a temporarily fixed state. Finally, the circuit surface of the semiconductor package is peeled off from the photo-curable adhesive layer, and the semiconductor package is picked up.

[0006] According to the method for manufacturing an electronic component device described in Patent Document 1, when the semiconductor package and protective adhesive tape are processed into small pieces, the circuit surface of the semiconductor package can be protected by covering it with the protective adhesive tape. The protective adhesive tape can then be removed by peeling the circuit surface of the semiconductor package from the photocurable adhesive layer of the protective adhesive tape fixed to the temporary fixing tape. The peel force required to remove the photocurable adhesive layer (protective layer) of the protective adhesive tape is weakened by the curing of the photocurable adhesive layer by light irradiation. Furthermore, heat generated when forming a metal film on a portion of the surface of the semiconductor package generates shrinkage stress (residual strain) within the substrate, which can easily deform the substrate due to the shrinkage stress (residual strain), making the peeling more likely to occur.

[0007] Japanese Patent Application Publication No. 2021-147579

[0008] However, in the manufacturing method of an electronic component device described in Patent Document 1, for example, the peeling speed must be adjusted to prevent the circuit surface from being damaged by the peeling force when peeling between the circuit surface of the semiconductor package and the photocurable adhesive layer (protective layer), and the process of removing the protective layer is not necessarily simple. Furthermore, the use of temporary fixing tape for the above-mentioned peeling can make the process of removing the protective layer complicated. Furthermore, after peeling, a portion of the photocurable adhesive layer (protective layer) may remain on the circuit surface, making it difficult to remove the photocurable adhesive layer (protective layer). Even if the photocurable adhesive layer (protective layer) overlapping the non-circuit surface where no circuit surface is formed is removed, the above-mentioned problems can occur.

[0009] Therefore, there is a demand for a surface protection composition that not only can protect at least one surface of a substrate by covering the surface when the substrate is processed, etc., but also can form a protective layer that can be relatively easily removed from the protected surface after processing, etc. In particular, there is a demand for a surface protection composition that can form a protective layer that can be relatively easily removed by at least partially dissolving when it comes into contact with a solvent such as water.

[0010] However, it cannot be said that sufficient research has yet been conducted into surface protection compositions that can not only cover at least one surface of a substrate to be protected and protect such surface, but also form a protective layer that can be relatively easily removed by contact with a liquid containing water after protection.

[0011] Therefore, an object of the present invention is to provide a surface protection composition for forming a protective layer that covers and protects at least one surface of a substrate in an electronic component device to be manufactured and that is then relatively easily removed upon contact with a liquid containing water. Another object of the present invention is to provide a surface protection sheet including a protective layer formed from the surface protection composition. Another object of the present invention is to provide a method for manufacturing an electronic component device using the protective layer.

[0012] In order to solve the above-mentioned problems, the surface protective composition of the present invention is a surface protective composition for protecting at least one surface of a substrate, and includes a polymer having a hydrophilic group in its molecule and a compound that generates an acid or a base upon at least one of heating and irradiation with active energy rays.

[0013] The surface protective sheet according to the present invention comprises a protective layer formed from the above-described surface protective composition.

[0014] The method for manufacturing an electronic component device according to the present invention includes the steps of: protecting at least one of the surfaces to be protected of both surfaces of a substrate by overlaying a protective layer formed from a surface protection composition on the surface to be protected; and removing the protective layer overlaid on the surface to be protected, wherein the surface protection composition includes a polymer having a hydrophilic group in its molecule and a compound that generates an acid or a base upon at least one of heating or irradiation with active energy rays; and in the removing step, the acid or the base is generated from the compound by heating or irradiation with active energy rays, thereby increasing the hydrophilicity of the protective layer, and the protective layer is removed by dissolving at least a portion of the protective layer in a liquid containing water.

[0015] 1 is a schematic cross-sectional view of an example of a surface protection sheet of the present embodiment, cut in the thickness direction; FIG. 2 is a schematic cross-sectional view showing an example of a wetting step in the manufacturing method for an electronic component device of the present embodiment; FIG. 3 is a schematic cross-sectional view showing an example of a protecting step in the manufacturing method for an electronic component device of the present embodiment; FIG. 4 is a schematic cross-sectional view showing an example of a protecting step in the manufacturing method for an electronic component device of the present embodiment; FIG. 5 is a schematic cross-sectional view showing an example of a state before a substrate is cleaved in the manufacturing method for an electronic component device of the present embodiment; FIG. 6 is a schematic cross-sectional view showing an example of a state after a substrate is cleaved in the manufacturing method for an electronic component device of the present embodiment; FIG. 7 is a schematic cross-sectional view showing an example of a removing step in the manufacturing method for an electronic component device of the present embodiment; FIG. 8 is a schematic cross-sectional view showing an example of a removing step in the manufacturing method for an electronic component device of the present embodiment; FIG. 9 is a cross-sectional view of an example of a dicing tape cut in the thickness direction; FIG. 10 is a cross-sectional view of an example of a dicing die bond film cut in the thickness direction; FIG. 11 is a cross-sectional view showing a state after a mounting step and a protecting step in the first embodiment; FIG. 12 is a cross-sectional view showing a state during a blade dicing processing step in the first embodiment. 1 is a cross-sectional view schematically showing a state after a blade dicing process has been performed in the first embodiment. FIG. 2 is a cross-sectional view schematically showing a state of a removal process in the first embodiment. FIG. 3 is a cross-sectional view schematically showing a state of a removal process in the first embodiment. FIG. 4 is a cross-sectional view schematically showing a state of a pick-up process in the first embodiment. FIG. 5 is a cross-sectional view schematically showing a state of a bonding process in the first embodiment. FIG. 6 is a cross-sectional view schematically showing a state of half-cutting a semiconductor wafer in another example of the first embodiment. FIG. 7 is a cross-sectional view schematically showing a state of half-cutting a semiconductor wafer in another example of the first embodiment. FIG. 8 is a cross-sectional view schematically showing a state of half-cutting a semiconductor wafer in another example of the first embodiment. FIG. 9 is a cross-sectional view schematically showing a state of a mounting process in another example of the first embodiment. FIG. 10 is a cross-sectional view cut in the thickness direction of an example of a semiconductor wafer. FIG. 11 is a cross-sectional view cut in the thickness direction of an example of a semiconductor chip produced by dividing a semiconductor wafer. FIG. 12 is a cross-sectional view schematically showing a state before a mounting process in the second embodiment. FIG. 13 is a cross-sectional view schematically showing a state of a mounting process in the second embodiment. 10A and 10B are cross-sectional views each showing a state after a mounting process in the second embodiment, a protection process in the second embodiment, and a stealth processing process in the second embodiment.10A and 10B are cross-sectional views schematically showing an expanding step in a second embodiment; a cross-sectional view schematically showing a removing step in a second embodiment; a cross-sectional view schematically showing a removing step in a second embodiment; a cross-sectional view schematically showing a pick-up step in a second embodiment; a cross-sectional view schematically showing a bonding step in a second embodiment; a cross-sectional view schematically showing a semiconductor wafer and a backgrind tape in a third embodiment; a cross-sectional view schematically showing a protection step in a third embodiment; a cross-sectional view schematically showing a state before a mounting step in a third embodiment; a cross-sectional view schematically showing a state of a mounting step in a third embodiment; a cross-sectional view schematically showing a state of a semiconductor wafer and a backgrind tape in a fourth embodiment; a cross-sectional view schematically showing a state of a stealth processing step in a fourth embodiment; a cross-sectional view schematically showing a state of a protection step in a fourth embodiment; a cross-sectional view schematically showing a state before a mounting step in a fourth embodiment; a cross-sectional view schematically showing a state of a mounting step in a fourth embodiment. 13A and 13B are cross-sectional views schematically showing a state of grinding after a protection process in the fifth embodiment. 13B are cross-sectional views schematically showing a state after grinding in the fifth embodiment. 13C are cross-sectional views schematically showing a state during a stealth processing process in the fifth embodiment. 13D are cross-sectional views schematically showing a state after a stealth processing process in the fifth embodiment.

[0016] Hereinafter, embodiments of the surface protective composition, surface protective sheet, and method for manufacturing electronic component devices according to the present invention will be described in order with reference to the drawings.

[0017] The surface protecting composition of this embodiment is a surface protecting composition for protecting at least one surface of a substrate, and includes a polymer having a hydrophilic group in its molecule and a compound that generates an acid or a base upon at least one of heating and irradiation with active energy rays (hereinafter also referred to as an ion-generating compound). The surface protecting composition of this embodiment is used, for example, to form a protective layer that protects at least one surface of a substrate to be protected (hereinafter also referred to as a surface to be protected).

[0018] By overlaying a protective layer formed from the surface-protecting composition on at least one surface of a substrate, adhesion of foreign matter to the surface of the substrate to be protected (the surface to be protected) can be prevented until the protective layer overlying the surface is removed. For example, when the substrate and the protective layer are fragmented while the protective layer formed from the surface-protecting composition and the substrate are overlapped, foreign matter such as fragments that may be generated during fragmentation can be prevented from adhering to the surface to be protected, thereby protecting the surface to be protected. Furthermore, by subjecting the protective layer to a heat treatment or active energy ray irradiation treatment, an acid or base is generated from the compound. This increases the hydrophilicity of the protective layer formed from the surface-protecting composition. At least a portion of the protective layer with increased hydrophilicity can be dissolved relatively easily in a liquid containing water upon contact with the liquid. Therefore, all or a portion of the protective layer with increased hydrophilicity dissolves in a liquid containing water, and the protective layer is easily detached from the surface to be protected. Therefore, the protective layer can be more easily removed from the surface to be protected than, for example, when a release tape is attached to the protective layer and the protective layer is removed together with the release tape. In particular, when removing a protective layer that has been divided into small pieces, the multiple small pieces of the protective layer can be more easily removed from the surface to be protected than when using a release tape. In this way, the protective layer formed from the above-mentioned surface protective composition can not only protect the surface to be protected of the substrate, which is a member of the electronic component device to be manufactured, but also, after protection, can be relatively easily removed from the surface to be protected by a liquid containing water.

[0019] In this embodiment, the hydrophilic group of the polymer is, for example, a hydroxy group or a carboxy group. The hydrophilic group may be a polyoxyethylene chain. In this embodiment, the ion-generating compound is, for example, an acid generator that generates an acid upon at least one of heating or irradiation with active energy rays, or a base generator that generates a base upon at least one of heating or irradiation with active energy rays. Examples of the ion-generating compound include a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator.

[0020] Because the surface protection composition contains the ion-generating compound, it has properties that increase its hydrophilicity upon at least one of a heat treatment and an irradiation treatment of active energy rays such as ultraviolet rays. The surface protection composition only needs to have a predetermined level of hydrophilicity or higher after the treatment. Therefore, before the treatment, the surface protection composition may have a hydrophilicity less than a predetermined level, or may have a hydrophilicity greater than a predetermined level. When the surface protection composition has a hydrophilicity greater than a predetermined level, typically, at least a portion of the surface protection composition dissolves in a liquid containing water. The ion-generating compound is preferably an ion-generating compound that generates an acid or a base upon irradiation with active energy rays (particularly ultraviolet rays).

[0021] The surface protective composition after the hydrophilicity has been increased by the above-mentioned treatment preferably has a predetermined level of hydrophilicity or more, that is, the water absorption rate of the surface protective composition is preferably 1.5% by mass or more. This makes the surface protective composition that has been subjected to a heat treatment or active energy ray irradiation treatment more soluble in a liquid containing water. The water absorption rate can be increased, for example, by increasing the content of the ion-generating compound in the surface protective composition. The water absorption rate may be, for example, 10.0% by mass or less. Note that when the hydrophilicity of the surface protective composition is increased by active energy ray irradiation treatment, the water absorption rate is 500 mJ / cm or more when the surface protective composition is heated or irradiated with a high-pressure mercury lamp. ２ The values ​​are those after the irradiation treatment.

[0022] The water absorption of the surface protective composition before the above-described heat treatment or active energy ray irradiation treatment may be less than 1.5% by mass. This prevents the protective layer from being unintentionally removed even if the protective layer comes into contact with water before the removal step (described in detail later) of removing the protective layer formed from the surface protective composition. Meanwhile, the water absorption of the surface protective composition before the above-described heat treatment or active energy ray irradiation treatment may be 0.1% by mass or more. This allows the surface protective composition subjected to the heat treatment or active energy ray irradiation treatment to have higher hydrophilicity. The water absorption of the surface protective composition before the above-described treatment can be increased, for example, by increasing the hydrophilic group of the polymer contained in the surface protective composition.

[0023] The water absorption of the surface protective composition is determined from measurements using coulometric titration according to the Karl Fischer method. Measurements are performed using the surface protective composition before and after the heating treatment or active energy ray irradiation treatment described above. Specifically, a test sample that has reached a steady state in an environment of 23°C and 50% RH is heated at 150°C for 3 minutes using a moisture vaporizer, and the vaporized moisture is measured. The water absorption is determined from the ratio of the measured moisture content to the mass of the test sample after heating. If the surface protective composition contains a solvent, the solvent is removed by evaporation or the like before the water absorption of the surface protective composition is measured.

[0024] For example, the surface protection composition of this embodiment includes, as the above-mentioned polymer, a polymer having a main chain and multiple side chains in the molecule, and each of the multiple side chains has at least one of an ester group or a hydrophilic group, and the hydrophilic group may be a hydroxy group or a carboxy group.

[0025] The polymer contains at least one of a hydroxy group and a carboxy group as a hydrophilic group in its molecule, and the hydroxy group or carboxy group allows the protective layer formed from the surface protection composition to adhere more sufficiently to the surface to be protected. Therefore, the protective layer can adhere sufficiently to the surface to be protected before being subjected to a treatment such as heating or irradiation with active energy rays, and after the treatment, the protective layer can be removed from the surface to be protected relatively easily as described above.

[0026] The polymer has a main chain and side chains in its molecule. The main chain is a covalently bonded chain formed, for example, by a radical polymerization reaction. For example, the main chain is a covalently bonded chain formed by a polymerization reaction of vinyl acetate (vinyl acetate), alkyl (meth)acrylate ((meth)acrylic acid alkyl ester), hydroxyalkyl (meth)acrylate ((meth)acrylic acid hydroxyalkyl ester), (meth)acrylic acid, or the like.

[0027] Each of the multiple side chains contains at least one of a hydrophilic group and an ester group. For example, among the many side chains contained in the above polymer, some side chains have hydrophilic groups and others have ester groups. The hydrophilic group is, for example, at least one of a hydroxy group and a carboxy group. The ester group is represented by -C(=O)-O-. In the ester group, the carbon atom may be positioned closer to the main chain than the oxygen atom of the ether group, or may be positioned farther from the main chain than the oxygen atom of the ether group. In other words, the side chain may have, from the main chain to the end of the side chain, an atomic arrangement of an ester group, -C(=O)-O-, or an atomic arrangement of an ester group, -O-(C=O)-.

[0028] In each side chain containing a hydrophilic group, the hydrophilic group may be located at the terminal portion of the side chain or at the center portion of the side chain. The hydrophilic group in the side chain is preferably located at the terminal portion of the side chain. The hydrophilic group located at the terminal portion of the side chain may be bonded to the main chain via an ester group. For example, the ester group, alkyl group, and hydrophilic group may be arranged in this order from the main chain to the terminal of the side chain.

[0029] In the side chain containing an ester group, the ester group is preferably located in the center of the side chain. Preferably, in the side chain, an alkyl group having 1 to 4 carbon atoms is bonded to the main chain via the ester group.

[0030] Examples of the polymer include polyvinyl alcohol obtained by hydrolyzing a portion of the ester bond in a vinyl acetate polymer, a copolymer of an alkyl (meth)acrylate and at least one of (meth)acrylic acid or a hydroxyalkyl (meth)acrylate, and polyethylene oxide (e.g., molecular weight of 50,000 or more). In this specification, the term "(meth)acrylate" encompasses both acrylate and methacrylate. Similarly, the term "(meth)acrylic acid" encompasses both acrylic acid and methacrylic acid.

[0031] When the polymer is polyvinyl alcohol (PVA), the degree of saponification (mol %) of the polyvinyl alcohol may be 20 or more and 100 or less before the protective layer formed from the surface protective composition is subjected to a heat treatment or active energy ray irradiation treatment (described in detail later). The degree of saponification of the polyvinyl alcohol is preferably 25 or more, and more preferably 35 or more. By increasing the degree of saponification of the polyvinyl alcohol, the protective layer formed from the surface protective composition will have higher hydrophilicity after the heat treatment or active energy ray irradiation treatment. Therefore, the protective layer can be more easily removed with a liquid containing water. On the other hand, the degree of saponification of the polyvinyl alcohol is preferably 80 or less, and more preferably 60 or less. By decreasing the degree of saponification of the polyvinyl alcohol, the adhesion to the substrate can be further improved.

[0032] <Method and conditions for measuring the degree of saponification> The degree of saponification is measured by proton magnetic resonance spectroscopy ( １The surface protective composition is measured by 1H NMR. If the surface protective composition contains components other than PVA, the PVA is separated and extracted by methanol extraction or the like before the measurement to avoid overlapping peaks in the measurement chart. Analytical device: FT-NMR (for example, "AVANCEIII-400" manufactured by Bruker Biospin) Observation frequency: 400 MHz (1H) Measurement solvent: deuterated water or deuterated dimethyl sulfoxide (deuterated DMSO) Measurement temperature: 80°C Chemical shift reference: External standard TSP-d4 (0.00 ppm) (when measuring deuterated water): Measurement solvent (2.50 ppm) (when measuring deuterated DMSO)

[0033] <Calculation of Saponification Degree> The saponification degree is calculated by the following calculation formula based on the peaks derived from the methylene group of the vinyl alcohol unit (VOH) (heavy water: 2.0 to 1.1 ppm, heavy DMSO: 1.9 to 1.0 ppm) and the peaks derived from the acetyl group of the vinyl acetate unit (VAc) (heavy water: around 2.1 ppm, heavy DMSO: around 2.0 ppm). In the following calculation formula, VOH(-CH ２ -) is the intensity of the peak derived from the methylene group of the vinyl alcohol unit (VOH), and VAc (CH ３ CO-) is the intensity of the peak derived from the acetyl group of the vinyl acetate unit (VAc).

[0034] The average degree of polymerization of the polyvinyl alcohol is preferably 100 or more, more preferably 200 or more. The average degree of polymerization is preferably 1000 or less, more preferably 800 or less. When the average degree of polymerization of the polyvinyl alcohol is 200 or more, it becomes easier to form a protective layer using the surface protection composition. On the other hand, when the average degree of polymerization of the polyvinyl alcohol is 1000 or less, the hydrophilicity of the polyvinyl alcohol is increased, and the protective layer formed from the surface protection composition becomes more easily soluble in a liquid containing water.

[0035] The average degree of polymerization is determined by the following measurement method and measurement conditions: <Method and conditions for measuring average degree of polymerization> Analytical apparatus: Gel permeation chromatography analyzer (for example, Agilent's "1260Infinity") Column: TSKgel G6000PWXL and TSKgel G3000PWXL (Tosoh's serially connected) Column temperature: 40°C Eluent: 0.2 M aqueous sodium nitrate solution Flow rate: 0.8 mL / min Injection volume: 100 μL Detector: Differential refractometer (RI) Standard samples: PEG standard sample and PVA standard sample By GPC measurement using the PEG standard sample, the mass average molecular weight Mw of the sample to be measured (PVA) and the PVA standard sample with a known average degree of polymerization are calculated. A calibration curve is created from the average degree of polymerization of the PVA standard samples and the calculated mass average molecular weight Mw of the PVA standard samples. Using this calibration curve, the average degree of polymerization of the sample (PVA) to be measured is calculated from the mass average molecular weight Mw of the sample (PVA).

[0036] The compound (ion-generating compound) contained in the surface protection composition of this embodiment is a compound that newly generates an acid or a base by at least one of a heat treatment and an active energy ray irradiation treatment. The ion-generating compound is preferably a compound that newly generates an acid, since the generated acid ionizes the hydrophilic group of the polymer, thereby easily increasing the hydrophilicity of the surface protection composition. The heat treatment and the active energy ray irradiation treatment will be described in detail later.

[0037] Examples of the ion-generating compound include photoion generators such as photoacid generators or photobase generators, and thermal ion generators such as thermal acid generators or thermal base generators, with the photoion generators being preferred. Note that a single compound may function as both a photoacid generator and a thermal acid generator. In other words, for example, a specific acid generator may generate an acid upon both heat treatment and active energy ray irradiation. The same applies to base generators. When the ion-generating compound is a photoacid generator, photobase generator, thermal acid generator, or thermal base generator, the protective layer formed from the surface-protecting composition generates an acid or a base more sufficiently upon heat treatment or active energy ray irradiation, such as ultraviolet light irradiation. This further enhances the hydrophilicity of the protective layer. Therefore, the protective layer can be more easily removed from the surface to be protected using a liquid containing water.

[0038] The photoacid generator as an acid generator is, for example, a photocationic polymerization initiator commonly used for cationic polymerization, and the thermal acid generator as an acid generator is, for example, a thermal cationic polymerization initiator commonly used for cationic polymerization. The photobase generator as a base generator is, for example, a photoanionic polymerization initiator commonly used for anionic polymerization, and the thermal base generator as a base generator is, for example, a thermal anionic polymerization initiator commonly used for anionic polymerization. Commercially available products can be used as the photoacid generator, thermal acid generator, photobase generator, or thermal base generator.

[0039] Photoacid generators include ionic and nonionic types. Ionic photoacid generators have a cationic structure and an anionic structure. Examples of ionic photoacid generators, depending on the type of cationic structure, include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0040] Examples of the onium salt compound include onium salt compounds such as iodonium salt compounds, sulfonium salt compounds, oxime sulfonate compounds, and diazonium salt compounds. Of these, iodonium salt compounds or sulfonium salt compounds are preferred, and sulfonium salt compounds are more preferred.

[0041] Examples of iodonium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-fluorophenyl)iodonium triflate, diphenyliodonium hexafluorophosphate, etc. Other examples include the iodonium salt compounds used in the following examples.

[0042] Examples of sulfonium salt compounds include diphenyl[4-(phenylsulfanyl)phenyl]sulfonium=trifluorotris(pentafluoroethyl)-λ ５-phosphanide, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium adamantanecarboxylate trifluoroethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium methanesulfonate, triphenylsulfonium phenolsulfonate, triphenylsulfonium nitrate, triphenylsulfonium maleate, bis(triphenylsulfonium)maleate, triphenylsulfonium hydrochloride, triphenylsulfonium acetate, triphenylsulfonium trifluoroacetate, triphenylsulfonium salicylate, triphenylsulfonium benzoate, triphenylsulfonium hydroxide, etc. Other examples include the sulfonium salt compounds used in the following examples.

[0043] Examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, and (5-octylsulfonyloxyimino)-(4-methoxyphenyl)acetonitrile.

[0044] The diazonium salt compound may, for example, be 4-nitrobenzenediazonium tetrafluoroborate.

[0045] Examples of commercially available onium salt compounds include OPTOMER SP-150, OPTOMER SP-170, and OPTOMER SP-171 (all manufactured by ADEKA Corporation), UVE-1014 (manufactured by General Electronics Corporation), OMNICAT250 and OMNICAT270 (both manufactured by IGM Resin), IRGACURE290 (manufactured by BASF Corporation), SAN-AID SI-60L, SAN-AID SI-80L, and SAN-AID SI-100L (all manufactured by Sanshin Chemical Industry Co., Ltd.), CPI-100P, CPI-101A, and CPI-200K (all manufactured by San-Apro Ltd.), and the like.

[0046] Examples of the sulfonimide compound as a photoacid generator include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-normal-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalimide, N-(camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, and 4-methylphenylsulfonyloxy)diphenylmaleimide.

[0047] Examples of disulfonyldiazomethane compounds as photoacid generators include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0048] Other examples of photoacid generators include 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine.

[0049] Examples of the thermal acid generator include aryl diazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylsulfoxonium salts, pyridinium salts, quinolinium salts, isoquinolinium salts, sulfonic acid esters, and iron arene complexes.

[0050] The acid generator, such as a photoacid generator or a thermal acid generator, preferably has good compatibility with the polymer contained in the surface protective composition. The acid generator is preferably an ionic acid generator, more preferably an ionic photoacid generator. The acid generator is preferably a stronger acid.

[0051] Gas phase acidity [ΔG acid] can be used as an index showing the acid strength of an acid generator. Gas phase acidity is an index of acidity that minimizes the solvent effect. That is, gas phase acidity is an index showing the acidity in the gas phase.

[0052] The reactivity of an acid generator is affected by the type of counter anion (conjugate acid) contained in the acid generator. The gas phase acidity of the anion contained in the acid generator is preferably 280 [kJ / mol] or less, and more preferably 260 [kJ / mol] or less. The smaller this value, the stronger the acid.

[0053] Representative examples of each anion and its gas phase acidity include (CF ３ CF ２ ) ３ PF ３ － (Gas phase acidity: 256 [kJ / mol]), SbF ６ － (Gas phase acidity: 256 [kJ / mol]), PF ６ － (Gas phase acidity: 277 [kJ / mol]), BF ４ －(Gas phase acidity: 288 [kJ / mol]). The acid generator may be an anion (CF ３ CF ２ ) ３ PF ３ － or SbF ６ － An acid generator having the formula:

[0054] Gas phase acidity is defined by IUPAC as the Gibbs energy change associated with acid dissociation and can be calculated by known methods, such as those described in J. Am. Chem. Soc. 2000, 122, 5114-5124.

[0055] Examples of the photobase generator include heterocyclic group-containing radiation-sensitive base generators such as 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, N-(2-nitrobenzyloxycarbonyl)pyrrolidine, and 1-(anthraquinone-2-yl)ethylimidazole carboxylate. Other examples include 2-nitrobenzyl cyclohexyl carbamate, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine, triphenylmethanol, o-carbamoylhydroxylamide, o-carbamoyloxime, hexaamminecobalt(III) tris(triphenylmethylborate), 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate, acetophenone O-benzoyloxime, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, etc. Further examples include the photobase generators used in the following examples.

[0056] Examples of the thermal base generator include carbamate derivatives such as 1-methyl-1-(4-biphenylyl)ethylcarbamate, 1,1-dimethyl-2-cyanoethylcarbamate, and benzoylcyclohexylcarbamate; urea derivatives such as urea and N,N-dimethyl-N'-methylurea; dihydropyridine derivatives such as 1,4-dihydronicotinamide; and quaternary ammonium salts of organosilanes or organoboranes.

[0057] In the surface protecting composition, the amount of the ion-generating compound per 100 parts by mass of the polymer is preferably 1 part by mass or more, more preferably 3 parts by mass or more. This allows the protective layer formed from the surface protecting composition to have higher hydrophilicity after heat treatment or active energy ray irradiation treatment. The amount of the ion-generating compound per 100 parts by mass of the polymer is preferably 10 parts by mass or less. This more sufficiently prevents the ion-generating compound from remaining in the surface protecting composition.

[0058] The surface protection composition of this embodiment may further contain, in addition to the above-mentioned components, for example, a solvent, a surfactant, etc. Examples of the solvent include water or an organic solvent. As the organic solvent, a relatively volatile organic solvent is preferable. Examples of such organic solvents include ethanol and methanol.

[0059] The surface protecting composition of this embodiment may be a solid having no fluidity, or may have fluidity. When the surface protecting composition contains a solvent, it may have fluidity.

[0060] The surface protection composition of this embodiment can be produced by mixing the above-mentioned polymer, the above-mentioned ion-generating compound such as the photoacid generator, and, if necessary, a solvent, etc., by a common method. Alternatively, the surface protection composition of this embodiment may be produced by volatilizing the solvent after the above-mentioned mixing.

[0061] The surface protecting composition of this embodiment is used, for example, to produce a surface protecting sheet, which will be described later.

[0062] Next, the surface protection sheet 10 of this embodiment will be described.

[0063] The surface protection sheet 10 of this embodiment includes at least a protective layer 11, as shown in Figure 1. The surface protection sheet 10 of this embodiment may further include a release liner 15 that overlaps at least one surface of the protective layer 11. The release liner 15 may be overlapped on one or both surfaces of the protective layer 11. Note that each figure in the drawings is a schematic view, and the aspect ratio is not necessarily the same as that of the actual product. The same applies to the other drawings.

[0064] In this embodiment, the protective layer 11 of the surface protective sheet 10 is formed into a sheet from the above-described surface protecting composition. When the surface protective sheet 10 is used, for example, the release liner 15 is peeled off from the protective layer 11, and the protective layer 11 is attached to at least one surface (the surface to be protected) of a substrate.

[0065] The protective layer 11 has flexibility that allows it to be deformed by a relatively weak force, and also has adhesiveness that allows it to adhere to the surface of the substrate to be protected, for example.

[0066] The protective layer 11 may be formed, for example, by applying the solvent-containing surface protective composition to one side of a substrate and then volatilizing the solvent. Alternatively, the protective layer 11 may be formed by applying the solvent-containing surface protective composition to one side of a release liner 15 and then volatilizing the solvent. The formed protective layer 11 preferably does not contain a solvent blended to impart fluidity to the surface protective composition. The protective layer 11 may be formed, for example, from the solvent-free surface protective composition by a general molding method.

[0067] In the surface protection sheet, the thickness of the protective layer 11 is not particularly limited, but is, for example, 1 μm or more and 100 μm or less. Such a thickness may be 3 μm or more, or 5 μm or more. Also, such a thickness may be 40 μm or less. Note that when the protective layer 11 is a laminate, the above thickness is the total thickness of the laminate.

[0068] The protective layer 11 may have physical properties that allow it to be diced into small pieces by being stretched in the plane direction. Protective layer 11 having such physical properties is preferably used when manufacturing electronic component devices through a stealth processing step using a stealth dicing device, which will be described later. Similarly, it is preferably used when manufacturing electronic component devices through a DBG process (described in detail later). Note that the protective layer 11 may also be preferably used when manufacturing electronic component devices through a blade dicing processing step (described in detail later), and therefore does not need to have such physical properties.

[0069] The adhesion of the protective layer 11 to the substrate is indicated, for example, by the peel force when peeling the protective layer 11 from a bare silicon wafer as a substrate. The peel force of the protective layer 11 at 25°C may be 10.0 [N / 10 mm] or less, or may be 8.0 N / 10 mm or less. The peel force may be 0.01 [N / 10 mm] or more. The peel force values ​​are values ​​before the protective layer 11 is subjected to at least one of a heat treatment and an active energy ray irradiation treatment.

[0070] The peel force is measured under the following measurement conditions. To measure the peel force of one surface of the protective layer 11 (the surface to be attached to a bare silicon wafer), a measurement sample is prepared as follows. First, a backing tape is attached to the surface of the protective layer 11 opposite to the one surface at 25°C using a hand roller. Next, the measurement sample is processed to a width of 100 mm, and a bare wafer is attached to the one surface of the protective layer 11. The attachment is performed under conditions of 90°C and 10 mm / sec. Then, in an atmosphere of 23°C, the protective layer 11 together with the backing tape is peeled from the bare wafer at a peel angle of 180° and a peel rate of 300 mm / min, and the peel force is measured. Finally, the measured value is converted to be expressed in units of [N / 10 mm]. An Autograph (manufactured by Shimadzu Corporation), for example, can be used as the measurement device.

[0071] The surface free energy of the protective layer 11 is 70 mJ / m at 25°C. ２] or less, and 65 [mJ / m ２ The surface free energy may be 20 [mJ / m ２ ] or more. When the surface free energy is within the above range, the water wettability of the protective layer 11 becomes suitably good, and therefore the protective layer 11 can be more easily removed in the removal step described below. The above surface free energy value is the value before the protective layer 11 is subjected to at least one of a heat treatment and an active energy ray irradiation treatment.

[0072] The protective sheet 1 of this embodiment is used, for example, during the process of manufacturing an electronic component device. Specifically, the protective sheet 1 of this embodiment is used for purposes such as temporarily protecting the surface to be protected (the surface to be protected) of an electronic component (a type of substrate). More specifically, the protective sheet 1 of this embodiment is used, for example, by being attached to the surface to be protected of the electronic component (a type of substrate). Examples of the electronic component include substrates such as semiconductor wafers, semiconductor chips, and wired circuit boards, connected wired circuit boards formed by connecting multiple wired circuit boards, and pseudo wafers.

[0073] The semiconductor chip typically includes a semiconductor chip body and electrode portions disposed on one or both sides of the semiconductor chip body and electrically connected to electrode portions of another component. Examples of such other components include a wiring circuit board or another semiconductor chip. The semiconductor chip may have a circuit surface on at least one side. Specifically, the semiconductor chip may be a TSV (Through Silicon Via) type semiconductor chip having paired electrode portions disposed on both sides of the semiconductor chip body and a conductive portion penetrating the semiconductor chip body in the thickness direction to electrically connect the electrode portions. A TSV type semiconductor chip may have a circuit surface formed on only one side, or may have a circuit surface formed on both sides. The circuit of the semiconductor chip may also include a sensor element (e.g., a light-receiving element or a vibration element) as an element. An example of such a semiconductor chip is a sensor chip. Examples of sensor chips include a CMOS (Complementary Metal-Oxide Semiconductor) chip and a MEMS (Micro Electron Systems) chip.

[0074] The pseudo wafer includes, for example, a support substrate and a package body in which a plurality of semiconductor chips arranged on the support substrate are collectively sealed with resin. The pseudo wafer may be the package body removed from the support substrate. A rewiring layer may be formed on at least a portion of the surface of the pseudo wafer. The protective sheet 1 may be used to cover the rewiring layer. Note that the divided bodies obtained by dividing the pseudo wafer into constituent units each including at least one semiconductor chip may be electronic components.

[0075] As described above, there are various types of electronic components having a surface to be protected (a surface to be protected), and various electronic components can serve as the substrate.

[0076] Next, a method for manufacturing the electronic component device of this embodiment will be described.

[0077] The method for manufacturing an electronic component device of this embodiment includes: a step of protecting at least one of the surfaces to be protected of the two surfaces of a substrate by overlaying a protective layer 11 formed from a surface protection composition on the surface to be protected (protection step); and a step of removing the protective layer 11 overlaid on the surface to be protected (removal step), wherein the surface protection composition includes a polymer having a hydrophilic group in its molecule and a compound (the above-mentioned ion-generating compound) that generates an acid or a base upon at least one of heating or irradiation with active energy rays, and in the removal step, the acid or the base is generated from the compound (ion-generating compound) upon heating or irradiation with active energy rays, thereby increasing the hydrophilicity of the protective layer 11, and the protective layer 11 is removed by dissolving at least a portion of the protective layer 11 in a liquid containing water.

[0078] The method for manufacturing an electronic component device according to this embodiment may further include a step of increasing the humidity of the gas in contact with the surface to be protected Sa (a wetting step) prior to the above-described protecting step (see FIG. 2A ). By carrying out the wetting step, it is possible to improve the adhesion of the protective layer 11 to the surface to be protected Sa. The wetting step can be carried out, for example, by bringing a gas containing water vapor into contact with the surface to be protected, spraying mist-like water onto the surface to be protected, or applying water to the surface to be protected.

[0079] In the protection step, as shown in Fig. 2B, the surface to be protected Sa of the substrate S may be protected using a surface protection sheet 10 having a release liner 15 on one side of the protective layer 11. For example, after the protective layer 11 of the surface protection sheet 10 is superimposed on the surface to be protected Sa of the substrate S, the release liner 15 may be peeled off from the protective layer 11 (see Fig. 2C).

[0080] 2D and 2E , the method for manufacturing an electronic component device according to this embodiment may further include a step of dividing the stack of overlapping substrates S and protective layers 11 into small pieces at intervals in the surface direction, thereby producing a plurality of stacked small pieces of chips S′ formed by dividing the substrates into small pieces and small pieces 11′ formed by dividing the protective layers into small pieces. Note that the substrate S before division may have weakened portions formed therein for the purpose of dividing the substrates into small pieces.

[0081] In the removing step, as shown in FIG. 2F, the plurality of small pieces 11' of the protective layer are subjected to, for example, a heat treatment or irradiation with active energy rays such as ultraviolet rays, thereby generating new acids or bases from the ion-generating compounds contained in each of the small pieces 11', and increasing the hydrophilicity of each of the small pieces 11'. Then, in the removing step, as shown in FIG. 2G, each small piece 11' of the protective layer overlapping the circuit surface of the chip S' is removed using a liquid containing water. The manufacturing method for an electronic component device of this embodiment may further include a step of placing the circuit surface of the chip S' facing the adherend and bonding the chip S' to the adherend.

[0082] The electronic component device manufactured by the manufacturing method of this embodiment includes at least one of the various electronic components described above. Examples of the electronic component device include a semiconductor device such as a semiconductor integrated circuit including a semiconductor chip, a device including a system LSI having a complementary metal oxide semiconductor (CMOS), or a device including a microelectromechanical system (MEMS) in which mechanical elements, sensors, actuators, or electronic circuits are integrated on a single silicon substrate, glass substrate, or organic material substrate using microfabrication technology. The manufactured electronic component device may also include a device including a wiring circuit board.

[0083] In the method for manufacturing an electronic component device according to this embodiment, at least one surface of the substrate is protected by a protective layer. The surface to be protected (hereinafter simply referred to as the protected surface) may be either one surface or both surfaces of the substrate. Circuit components (described in detail below) may or may not be disposed on the protected surface.

[0084] The substrate may be made of any material, as long as it is plate-shaped. Examples of the substrate material include glass, silicon, stainless steel (SUS), plastic, and ceramic. Examples of the substrate include a semiconductor wafer, a sensor wafer such as a CMOS or MEMS, a pseudo wafer, and a wiring circuit board.

[0085] In the above-mentioned protection step, a protective layer 11 may be overlaid on the surface of the substrate on which at least one of the circuit wiring, sensor unit, and electrode unit is arranged as a circuit component. For example, the protective layer 11 may be overlaid on one side (circuit surface) of the substrate on which the circuit wiring is arranged, the protective layer 11 may be overlaid on one side of the substrate on which the sensor unit is arranged, or the protective layer 11 may be overlaid on one side of the substrate on which the electrode unit is arranged. In the above-mentioned protection step, it is preferable to overlay the protective layer 11 on at least one side of the substrate so as to cover the circuit wiring, sensor unit, or electrode unit with the protective layer 11. Examples of circuit components include circuit wiring, electrode units, or elements such as transistors, diodes, or sensor units (such as light-receiving sensors or vibration sensors).

[0086] The following will describe in detail the case where a semiconductor integrated circuit (semiconductor device) is manufactured as an electronic component device.

[0087] Generally, a method for manufacturing a semiconductor device includes a front-end process in which a circuit surface is formed on one side of a wafer using highly integrated electronic circuits, and a back-end process in which chips are cut out from the wafer with the circuit surface formed and assembled.

[0088] In a post-process, for example, a wafer (semiconductor wafer) serving as a substrate with a circuit surface formed thereon is formed with fragile portions for dicing into small semiconductor chips (dies), and an adhesive layer of dicing tape is attached to the surface opposite the circuit surface. Then, while the semiconductor wafer remains attached to the adhesive layer of the dicing tape, the dicing tape is stretched in the planar direction, dicing the semiconductor wafer into semiconductor chips along the fragile portions. The resulting semiconductor chips are then peeled off from the adhesive layer of the dicing tape.

[0089] The above-mentioned post-processing includes, for example, a stealth processing step in which fragile portions for dicing the wafer into small chips (dies) are formed in the wafer using laser light or the like, a mounting step in which the surface of the semiconductor wafer opposite the circuit surface is attached to a dicing tape to fix the semiconductor wafer, an expanding step in which the semiconductor wafer is diced into semiconductor chips (dies) by stretching the dicing tape in the planar direction, a pick-up step in which the semiconductor chips are peeled off from the adhesive layer and removed, and a bonding step in which the removed semiconductor chips are bonded to an adherend. A semiconductor integrated circuit (semiconductor device) is manufactured through, for example, these steps.

[0090] In the manufacturing method of a semiconductor device (electronic component device) of this embodiment, for example, semiconductor chips are cut out from a semiconductor wafer on which a circuit surface is formed, and a semiconductor device having the cut-out semiconductor chips is assembled. In the manufacturing method of a semiconductor device of this embodiment, a semiconductor device is manufactured as follows using at least the protective layer 11 of the surface protective sheet 10 and a dicing tape 20 (see FIG. 3A). These sheets and tapes are used as auxiliary tools for manufacturing a semiconductor device. It is also possible to use a dicing die bond film in which a die bond sheet 30 is superimposed on the adhesive layer 22 of the dicing tape 20 (see FIG. 3B). Commercially available products can be used as the dicing tape 20 and the dicing die bond film.

[0091] Specific embodiments of the method for manufacturing a semiconductor device will be described in detail below, from the first embodiment to the fifth embodiment. Note that the drawings showing the manufacturing method of the first embodiment are marked with "I." Similarly, the second to fifth embodiments are marked with "II" to "V" in the drawings, respectively.

[0092] First Embodiment A method for manufacturing a semiconductor device according to a first embodiment includes an assembly process of cutting semiconductor chips X out of a semiconductor wafer W (substrate) on which a circuit surface is formed, and assembling a semiconductor device having such semiconductor chips X. The assembly process includes the steps of: protecting the circuit surface (protected surface) by overlaying a protective layer 11 for protecting the circuit components on at least one surface of the semiconductor wafer W, which is the circuit surface on which any of the circuit components is formed; dividing the stack of overlapping semiconductor wafers W and protective layer 11 into small pieces at intervals in the surface direction to produce a plurality of small pieces of a stack in which semiconductor chips X obtained by dicing the semiconductor wafer W and small pieces 11' of the protective layer are overlapped; subjecting each small piece 11' of the protective layer overlaying the circuit surface of the semiconductor chip X to a heat treatment or active energy ray irradiation treatment or the like to generate an acid or base from the ion-generating compound in each small piece 11' to increase the hydrophilicity of each small piece 11', and then removing each small piece 11' of the protective layer with a liquid containing water; and bonding the semiconductor chip X to the adherend.

[0093] The assembly process of the first embodiment includes, for example, the following steps. Specifically, the assembly process of the first embodiment includes a mounting process in which a semiconductor wafer W having circuit components formed on one side thereof is attached to a dicing die bond film (a die bond sheet 30 superimposed on a dicing tape 20) and the semiconductor wafer W is fixed to the dicing die bond film; a protection process in which a protective layer 11 is attached to the circuit side of the semiconductor wafer W to protect the circuit side; a blade dicing process (a process for producing a plurality of small pieces of the laminate) in which the semiconductor wafer W to which the die bond sheet 30 and the protective layer 11 are attached is diced with a dicing blade T or the like to produce semiconductor chips (dies) obtained by dicing the semiconductor wafer W; a removal process (the above-mentioned removing process) in which a plurality of small pieces 11' of the protective layer attached to the semiconductor chip X are removed after the above-mentioned heating treatment or active energy ray irradiation treatment; and a pick-up process in which the semiconductor chip X and the small pieces 30' of the die bond sheet are peeled off from each other to take out the semiconductor chip X with the small pieces 30' of the die bond sheet attached. and a bonding step (the above-mentioned bonding step) of bonding the extracted semiconductor chip X to an adherend via the die-bonding sheet piece 30'. When these steps are carried out, the above-mentioned protective layer 11 and the dicing die-bonding film having the dicing tape 20 are used as manufacturing aids.

[0094] The semiconductor wafer W is configured to obtain a plurality of semiconductor chips X. Specifically, the semiconductor wafer W is configured to be divided into small pieces at intervals in a plurality of directions along the surface (for example, directions along the surface that are perpendicular to each other), so that a plurality of semiconductor chips X can be fabricated. Furthermore, the semiconductor wafer W has a circuit surface on at least one surface on which at least one type of circuit component is arranged. For example, the semiconductor wafer W used in the first embodiment has a circuit surface formed on one of its surfaces.

[0095] In recent years, with the further advancement of integration technology in the semiconductor industry, thinner semiconductor chips (e.g., thicknesses of 20 μm to 50 μm) are desired. When viewed from one side in the thickness direction, the semiconductor chip has, for example, a rectangular shape, with a side length of, for example, 5 mm to 20 mm.

[0096] In the mounting step, as shown in FIG. 4A, a dicing ring R is attached to the adhesive layer 22 of the dicing tape 20, and a semiconductor wafer W is attached and fixed to a die bond sheet 30 that is superimposed on the dicing tape 20.

[0097] In the protection step, as shown in FIG. 4A , for example, a protective layer 11 is superimposed on one of the circuit surfaces of the semiconductor wafer W. In the protection step, for example, the protective layer 11 may be superimposed on the circuit surface by directly pressing and adhering the protective layer 11 to the circuit surface. Alternatively, a surface protection composition containing solid components constituting the protective layer 11 and a solvent that dissolves the solid components may be prepared, and the prepared surface protection composition may be applied to the circuit surface, followed by volatilizing the solvent to form the protective layer 11 in contact with the circuit surface, thereby superimposing the protective layer 11 on the circuit surface. By superimposing the protective layer 11 on the circuit surface of the semiconductor wafer W, the circuit surface can be protected by the protective layer 11 until the protective layer 11 is removed. Therefore, the adhesion of dust and the like to the circuit surface of the semiconductor wafer W covered with the protective layer 11 can be prevented. The protection step may be performed after the mounting step, or the mounting step may be performed after the protection step.

[0098] In the blade dicing process, the semiconductor wafer W is diced, as shown in FIGS. 4B and 4C . Specifically, the semiconductor wafer W is cut into a predetermined size together with the die bond sheet 30 to form semiconductor chips with the die bond sheet 30. The blade dicing process is performed using, for example, a dicing blade T according to a conventional method. For example, a cutting method called a full cut, in which the cut is made up to the die bond sheet 30, can be employed in the blade dicing process. The dicing device used in the blade dicing process is not particularly limited, and any conventionally known device can be used. In the blade dicing process, foreign matter such as debris may be generated when the semiconductor wafer W is cut. Since the protected surface of the semiconductor wafer W is protected by the protective layer 11, adhesion of foreign matter to the protected surface can be suppressed. Prior to the blade dicing process, a dicing ring R may be attached to the adhesive layer 22 of the dicing tape 20, and then the dicing ring R may be fixed to the holder H of the expanding device.

[0099] In the removal step, as shown in Fig. 4D, the plurality of small pieces 11' of the protective layer are subjected to a treatment to generate an acid or a base from the ion-generating compound. As such a treatment, at least one of a heat treatment and an active energy ray irradiation treatment is adopted. The heat treatment is carried out by exposing the plurality of small pieces 11' of the protective layer to an environment of 90°C or higher and 250°C or lower for 10 minutes or longer and 300 minutes or shorter. The active energy ray irradiation treatment is carried out, for example, at 10 mW / cm ２ More than 300mW / cm ２ The ultraviolet rays with the following intensity are used as active energy rays, and the cumulative light amount is 50 mJ / cm ２ More than 1000mJ / cm ２The plurality of small pieces 11' of the protective layer are irradiated with ultraviolet light as follows: In the removal process, by performing the above-described treatment on the plurality of small pieces 11' of the protective layer, an acid or a base is generated from the ion-generating compound contained in the small pieces 11'. The hydrophilicity of the plurality of small pieces 11' of the protective layer is increased by the amount of newly generated acid or base. As a result, when the small pieces 11' are later brought into contact with a liquid containing water, the small pieces 11' can be removed relatively easily from the surface of the semiconductor chip X.

[0100] In the removal process, as shown in FIG. 4E , the protective layer fragments 11′ are removed from the surface (protected surface) of the semiconductor chip X by contacting a liquid containing water with the protective layer fragments 11′ and dissolving at least a portion of each of the fragments 11′ in the liquid. By removing the protective layer fragments 11′ in this manner, all of the protective layer fragments 11′ can be removed relatively easily, and the liquid can also be used to relatively easily reduce the number of foreign particles adhering to the semiconductor chip surface. Furthermore, the surface (protected surface) of each semiconductor chip X on which the protective layer fragments 11′ overlap can also be cleaned with the liquid.

[0101] In the removal step, the protective layer pieces 11' may be removed by dissolving all of the fragmented protective layer (the plurality of protective layer pieces 11') in the liquid. Alternatively, the protective layer pieces 11' may be removed by dissolving some of the components of the protective layer pieces 11' in the liquid and peeling off each of the pieces 11', whose adhesion to the semiconductor chip X has weakened, from the semiconductor chip X.

[0102] The water-containing liquid is not particularly limited as long as it is a liquid substance containing water. Such a liquid may contain 30% by mass or more of water, 50% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more of water. The liquid may contain a component that dissolves in water in addition to water. Examples of such a component include water-soluble organic solvents. Examples of such water-soluble organic solvents include monohydric alcohols having 4 or less carbon atoms, such as methanol, ethanol, propanols such as isopropyl alcohol, and butanols such as t-butanol.

[0103] In the removal step in the first embodiment, the protective layer pieces 11' may be immersed in the stirred liquid to bring the liquid into contact with the protective layer pieces 11'. Alternatively, the liquid may be sprayed from a nozzle or the like to bring the protective layer pieces 11' into contact with the liquid. The temperature of the liquid is not particularly limited and may be set to, for example, 10°C or higher and 90°C or lower.

[0104] For example, in the removal step, the liquid is sprayed toward the semiconductor chips X attached to the die bond sheet pieces 30' while rotating a disk-shaped stage supporting the dicing tape 20 from below in the circumferential direction. This makes it possible to remove the multiple protective layer pieces 11' overlapping the semiconductor chips X. The rotation speed of the stage may be, for example, 500 rpm or more and 4000 rpm or less, the amount of liquid sprayed may be, for example, 0.05 L / min or more and 5.0 L / min or less, and the spraying time may be, for example, 5 seconds or more and 300 seconds or less.

[0105] According to the semiconductor device manufacturing method of the first embodiment, the protective layer 11 is superimposed on the surface (circuit surface) of the semiconductor wafer W on which the circuit components are formed, thereby protecting the circuit surface until the protective layer 11 is removed. Specifically, the semiconductor wafer W is diced into small pieces to produce the semiconductor chips X while the semiconductor wafer W and the protective layer 11 are superimposed. This prevents foreign matter, such as fragments that may be generated when the semiconductor wafer W is cleaved, from adhering to the circuit surface of the semiconductor chips X. Even if foreign matter is adhering to the circuit surface of the semiconductor chips X before the protective layer 11 is superimposed, the foreign matter can be removed when the small pieces 11' of the protective layer superimposed on the circuit surface of the semiconductor chips X are removed. Therefore, the adhesion of foreign matter to the circuit surface of the semiconductor chips X to be manufactured can be suppressed.

[0106] 4F, in the pick-up process, the semiconductor chip X is peeled off from the adhesive layer 22 of the dicing tape 20. More specifically, the pin members P are raised to push up the semiconductor chip X to be picked up through the dicing tape 20. The pushed-up semiconductor chip X is held by the suction jig J.

[0107] During the pickup process, the die bond sheet pieces 30' attached to the semiconductor chips X must be easily peeled from the adhesive layer 22 of the dicing tape 20. Furthermore, during the expanding process, the die bond sheet 30, the semiconductor wafer W, and the protective layer 11 must be efficiently separated into small pieces by stretching the dicing tape 20. The dicing tape 20 described above is designed to efficiently achieve this performance. For example, the dicing tape 20 is configured so that the adhesive layer 22 hardens and the adhesive strength of the adhesive layer 22 decreases when irradiated with active energy rays (e.g., ultraviolet rays). Since the adhesive layer 22 hardens after irradiation, the adhesive strength of the adhesive layer 22 can be reduced, allowing the semiconductor chips X and the die bond sheet pieces 30' to be relatively easily peeled from the adhesive layer 22 after irradiation. Dicing tapes 20 configured in this manner are commercially available.

[0108] In the bonding process, the semiconductor chip X with the die bond sheet piece 30' attached thereto is bonded to the adherend Z. In other words, the semiconductor chip X is bonded to the adherend Z via the die bond sheet piece 30'. Note that, in the bonding process, as shown in FIG. 4G, the semiconductor chips X with the die bond sheet piece 30' attached thereto may be stacked multiple times. In the first embodiment, the semiconductor chip X is bonded to the adherend, such as a substrate or semiconductor chip X, via the die bond sheet piece 30'. When stacking multiple semiconductor chips X as described above in the bonding process, the stacked semiconductor chips X are prevented from having foreign matter attached to their circuit surfaces, thereby reducing the number of foreign matter that gets between one stacked semiconductor chip X and the other stacked semiconductor chip X. Note that the adherend Z may be, for example, an interposer, a wired circuit board, or a small piece of a substrate (when small pieces of a substrate are stacked).

[0109] In the first embodiment, in order to protect the semiconductor chip X after the bonding step, a resin sealing step may be performed in which the semiconductor chip X is sealed (covered) with a thermosetting resin or the like.

[0110] In the above description of the first embodiment, an example was given in which the semiconductor wafer W was diced into small pieces by a blade dicing process. However, the semiconductor wafer W may also be diced into small pieces through a so-called DBG process, in which the thickness of the semiconductor wafer W is reduced after the semiconductor wafer W is half-cut. In the half-cut process, for example, grooves are formed in the semiconductor wafer W to process the semiconductor wafer W into chips (dies) by a fracturing process, and the semiconductor wafer W is then ground to reduce its thickness. In the half-cut process, as shown in FIGS. 4H to 4K, for example, a wafer processing tape E is applied to the surface of the semiconductor wafer W opposite the circuit surface. With the wafer processing tape E applied, a dividing groove is formed. A backgrinding tape B is applied to the surface with the grooves formed, while the wafer processing tape E that was initially applied is peeled off. With the backgrinding tape B applied, the semiconductor wafer W is ground until it reaches a predetermined thickness. Then, a mounting process is performed, and then a semiconductor device is manufactured in the same manner as described above.

[0111] Next, a second embodiment will be described in detail. Note that the second embodiment will not be described in the same manner as the first embodiment. In the second embodiment, unless otherwise specified, the same operations as in the first embodiment can be performed.

[0112] "Second Embodiment" A manufacturing method of a semiconductor device according to the second embodiment includes, for example, a mounting step of attaching a semiconductor wafer W having circuit components formed on both sides thereof to a dicing tape 20 and fixing the semiconductor wafer W to the dicing tape 20; a protection step of protecting the exposed circuit surface of the semiconductor wafer W by attaching a protective layer 11; a stealth processing step of preparing the semiconductor wafer W to be diced into semiconductor chips (dies) by forming fragile portions inside the semiconductor wafer W to which the protective layer 11 has been attached using laser light; an expanding step of dicing the semiconductor wafer W and the protective layer 11 together; a removal step of removing the plurality of small pieces 11' of the protective layer attached to the semiconductor chip X after the above-mentioned heating treatment or active energy ray irradiation treatment; a pick-up step of peeling the semiconductor chip X from the adhesive layer 22 to remove the semiconductor chip X; and a bonding step of bonding the removed semiconductor chip X to an adherend. When these steps are carried out, the above-described protective layer 11 and dicing tape 20 are used as manufacturing aids.

[0113] The dicing tape 20 used in the first embodiment can be used.

[0114] The semiconductor wafer W (substrate) before being diced into semiconductor chips X may be ground to a desired thickness by back-grinding, for example. Specifically, in the back-grinding, the semiconductor wafer W having a back-grinding tape B attached to its circuit surface may be ground to reduce the thickness of the semiconductor wafer W to the thickness of the semiconductor chips X to be fabricated later.

[0115] The semiconductor wafer W used in the second embodiment has a circuit surface formed on each of its two surfaces. On the other hand, the semiconductor wafer W used in the other embodiments has a circuit surface formed on one of its surfaces. As shown in Figures 5A and 5B, an electrode portion D is arranged on the surface on which the circuit surface is formed, and an electrode portion D is also arranged on the surface on which the circuit surface is formed. The electrode portion D on one surface is electrically connected to the electrode portion D on the other surface.

[0116] Specifically, the semiconductor chips X produced by dividing the semiconductor wafer W have electrode portions D arranged on both sides thereof and electrically connected to each other. More specifically, as shown in Fig. 5B, the electrode portions D are arranged on both sides of the semiconductor chip X, and conductive through vias V are arranged so as to penetrate the semiconductor chip X in the thickness direction. The electrode portions D on both sides are electrically connected to each other via the through vias V.

[0117] In the second embodiment, as shown in Fig. 6A, for example, a glass carrier G is attached to one circuit side of a semiconductor wafer W. The glass carrier G is placed on one circuit side of the semiconductor wafer W to support a relatively thin semiconductor wafer and facilitate handling of the semiconductor wafer. For example, after the one circuit side is formed, the glass carrier G is attached to the circuit side and used to arrange additional circuit components on the other side of the semiconductor wafer W. The thickness of the glass carrier G is, for example, 0.5 mm or more and 5.0 mm or less.

[0118] In the mounting step, a dicing ring R is attached to the adhesive layer 22 of the dicing tape 20, and a semiconductor wafer W is attached to the exposed surface of the adhesive layer 22 (see FIG. 6B). Next, the glass carrier G is peeled off from the semiconductor wafer W (see FIG. 6C).

[0119] In the subsequent protection step, a protective layer 11 is superimposed on one of the circuit surfaces of the semiconductor wafer W (see FIG. 6D ). In the protection step, for example, the protective layer 11 may be superimposed on the circuit surface by directly pressing and adhering the protective layer 11 against the circuit surface. Alternatively, a surface protection composition containing solid components constituting the protective layer 11 and a solvent that dissolves the solid components may be prepared, and the prepared surface protection composition may be applied to the circuit surface, followed by volatilizing the solvent to form the protective layer 11 in contact with the circuit surface, thereby superimposing the protective layer 11 on the circuit surface. By superimposing the protective layer 11 on the circuit surface of the semiconductor wafer W, the circuit surface can be protected by the protective layer 11 until the protective layer 11 is removed. This prevents dust and other foreign matter from adhering to the circuit surface of the semiconductor wafer W covered with the protective layer 11.

[0120] In the stealth processing step, weakened portions for dicing the semiconductor wafer W into semiconductor chips X are formed inside the semiconductor wafer W. The weakened portions are formed inside the semiconductor wafer W by irradiating the semiconductor wafer W with laser light L (see FIG. 6E ). The laser light L is irradiated onto the semiconductor wafer W from the dicing tape side, for example. Note that the laser light L is irradiated onto the semiconductor wafer W so that each semiconductor chip X, which is produced by dividing the semiconductor wafer W in a subsequent expanding step, has the electrode portion D as designed in advance. The stealth processing step can be performed, for example, using a commercially available stealth dicing device.

[0121] In the expanding process, as shown in FIG. 6F , with the dicing tape 20 and the protective layer 11 disposed on both sides of the semiconductor wafer W, the dicing tape 20 is stretched in the planar direction to increase its surface area. This divides the stack of the semiconductor wafer W and the protective layer 11 into small pieces, widening the spacing between adjacent semiconductor chips X formed by the small pieces along the planar direction. Specifically, a push-up member U provided in the expanding device pushes up the dicing tape 20 from below, stretching the dicing tape 20 so that it spreads in the planar direction. This causes the semiconductor wafer W and the protective layer 11 to be diced under specific temperature conditions. The temperature conditions are, for example, between −20°C and 0°C. The expanded state is released by lowering the push-up member U (this is the low-temperature expanding process). When performing the expanding process at such low temperatures, the protective layer 11 must be cleaved and diced into small pieces. The protective layer 11 described above is designed to be cleaved well during this process. Furthermore, in the expanding process, the dicing tape 20 is stretched under higher temperature conditions (e.g., 10°C or higher and 25°C or lower) to expand the surface area of ​​the dicing tape 20. This separates adjacent semiconductor chips X in the plane direction of the dicing tape 20, further widening the kerf (gap) (room-temperature expanding process). In the expanding process, the dicing tape 20 is stretched in the plane direction to expand the area of ​​the dicing tape 20, thereby dividing the protective layer 11 into small pieces along with the semiconductor wafer W. More specifically, by stretching the dicing tape 20, the semiconductor wafer W can be divided into small semiconductor chips X along the aforementioned fragile portions inside the semiconductor wafer. At this time, as the semiconductor wafer W is divided into small semiconductor chips X, the protective layer 11 is also divided into small pieces.

[0122] The removal step of the second embodiment can be carried out in the same manner as the removal step of the first embodiment, as shown in FIGS. 6G and 6H.

[0123] 6I, in the pick-up step of the second embodiment, the semiconductor chip X is peeled off from the adhesive layer 22 of the dicing tape 20. When the pick-up step is performed in this manner, the semiconductor chip X is peeled off from the adhesive layer 22 of the dicing tape 20.

[0124] As described above, the semiconductor chip X removed by the pick-up process has mutually conductive electrode portions D arranged on both sides. The electrode portions D and non-electrode portions other than the electrode portions D are arranged on the surface layers of one and the other sides of the semiconductor chip X. The non-electrode portions are made of, for example, an insulating material (silicon oxide). As shown in FIG. 5B , the surfaces of the electrode portions D and non-electrode portions are flush with each other on one and the other sides of the semiconductor chip X. The electrode portions D are formed, for example, to have a thickness of 5 nm to 10 μm from the surface of the semiconductor chip X. The through vias V, which are arranged to penetrate the semiconductor chip X in the thickness direction, are covered with the insulating material except for the portions in contact with the electrode portions D. In other words, a portion of the surface of the through vias V extending through the semiconductor chip X in the thickness direction is covered with the insulating material, and another portion is in contact with the electrode portions D.

[0125] The bonding step is performed after the removing step and the picking up step. In the bonding step, the semiconductor chip X may be bonded to the substrate with the surface (circuit surface) of the semiconductor chip X from which the small piece 11' of the protective layer has been removed facing the substrate, as shown in FIG.

[0126] In the bonding process, for example, a semiconductor chip X is bonded to an adherend Z (such as a wiring board). At this time, the adherend Z and the semiconductor chip X are bonded so that the electrode portions D of the adherend Z and the electrode portions D of the semiconductor chip X are electrically connected to each other. Furthermore, for example, in the bonding process, at least two semiconductor chips X are stacked, and the electrode portions D of one semiconductor chip X (the adherend) are directly connected to the electrode portions D of the other semiconductor chip X. When stacking multiple semiconductor chips X as described above in the bonding process, the stacked semiconductor chips X are prevented from having foreign matter attached to their circuit surfaces, thereby reducing the number of foreign matter that gets between one stacked semiconductor chip X and the other stacked semiconductor chip X. Therefore, the electrode portions D of adjacent semiconductor chips X can be more reliably connected to each other. Therefore, the circuits of the multiple semiconductor chips X are electrically connected to each other with high reliability.

[0127] For example, an atomic diffusion bonding process can be used to directly connect the electrode portions D. The atomic diffusion bonding process can be performed using, for example, a commercially available atomic diffusion bonding apparatus.

[0128] Next, the third to fifth embodiments will be described in detail. Note that for the third to fifth embodiments, the same explanation as for the first or second embodiment will not be repeated. In the third to fifth embodiments, unless otherwise specified, the same operations as those in the first or second embodiment can be performed.

[0129] The semiconductor device manufacturing method of the third embodiment includes the steps described above, similar to the semiconductor device manufacturing method of the second embodiment. However, the semiconductor device manufacturing method of the third embodiment differs from the second embodiment mainly in that circuit components are arranged on one surface of the semiconductor wafer W, and in that, in the mounting step, the semiconductor wafer W is attached to the adhesive layer 22 in a state where the semiconductor wafer W and the surface protection sheet 10 are stacked together, rather than the semiconductor wafer W placed on the glass carrier G being attached to the adhesive layer 22 of the dicing tape 20.

[0130] More specifically, in the method for manufacturing a semiconductor device according to the third embodiment, as shown in FIG. 7A, a semiconductor wafer W attached to a backgrind tape B is prepared.

[0131] 7B, in the protection step, the protective layer 11 of the surface protective sheet 10 is attached to the semiconductor wafer W. At this time, the protective layer 11 of the surface protective sheet 10 is attached to one surface of the semiconductor wafer W, and the backgrind tape B is attached to the other surface. A circuit surface is formed on the one surface of the semiconductor wafer W.

[0132] 7C , in the mounting step, the backgrind tape B is peeled off from the semiconductor wafer W while the semiconductor wafer W and the surface protection sheet 10 are overlapped with each other. As a result, the semiconductor wafer W and the surface protection sheet 10 are overlapped with each other, and the other surface of the semiconductor wafer W (the surface on which the circuit surface is not formed) is exposed.

[0133] 7D , in the mounting step of the third embodiment, with the semiconductor wafer W and the protective layer 11 overlapping each other, the other exposed surface of the semiconductor wafer W is attached to the adhesive layer 22 of the dicing tape 20. At this time, because the protective layer 11 and the release liner 15 are attached to one surface of the semiconductor wafer W, the semiconductor wafer W can be pressed against the adhesive layer 22 via the protective layer 11 and the release liner 15. Therefore, the circuit surface of the semiconductor wafer W can be attached to the adhesive layer 22 while protecting it.

[0134] In the mounting process, it is preferable to overlay the protective layer 11 on the semiconductor wafer W with the release liner 15 laminated on the protective layer 11, and to peel the release liner 15 from the protective layer 11 before the protective layer 11 is broken into small pieces in the expanding process.

[0135] In the third embodiment, steps not specifically mentioned can be performed in the same manner as the steps in the first to fifth embodiments.

[0136] Next, a fourth embodiment will be described in detail. Note that the same description as that of the above-described embodiments will not be repeated for the fourth embodiment. In the fourth embodiment, unless otherwise specified, the same operations as those in the first to third embodiments can be performed.

[0137] "Fourth Embodiment" The method for manufacturing a semiconductor device according to the fourth embodiment differs from the third embodiment mainly in that, before the mounting step, a laser beam is irradiated onto the semiconductor wafer W to form a fragile portion inside the wafer. Specifically, the method for manufacturing a semiconductor device according to the fourth embodiment includes a stealth processing step in which, in order to form the fragile portion, a laser beam is used to form a fragile portion inside the semiconductor wafer W to which the backgrind tape B has been attached, thereby preparing the semiconductor wafer W for dicing.

[0138] 8A, a semiconductor wafer W is prepared in a state where it is overlapped with a backgrind tape B. The semiconductor wafer W in this state is thinned to a desired thickness by, for example, performing a backgrinding process with the backgrind tape B still attached.

[0139] In the stealth processing step of the fourth embodiment, as shown in Fig. 8B, a laser beam is irradiated onto a semiconductor wafer W overlapping with a backgrind tape B. The backgrind tape B is attached, for example, to the surface of the semiconductor wafer W opposite to the circuit surface. The laser beam is irradiated from the circuit surface side of the semiconductor wafer W, for example.

[0140] In the protection step of the fourth embodiment, similarly to the third embodiment, as shown in Fig. 8C, the protective layer 11 of the surface protective sheet 10 is attached to the semiconductor wafer W. This results in the protective layer 11 overlapping one surface (circuit surface) of the semiconductor wafer W, and the backgrind tape B overlapping the other surface. Thereafter, the backgrind tape B is peeled off from the semiconductor wafer W. Note that a release liner 15 may overlap the protective layer 11, as shown in Fig. 8C.

[0141] Thereafter, as shown in FIGS. 8D and 8E, the mounting process can be carried out in the same manner as in the third embodiment.

[0142] In the fourth embodiment, steps not specifically mentioned can be performed in the same manner as the steps in the first to third embodiments.

[0143] Finally, the fifth embodiment will be described in detail. Note that the same description as in the first to fourth embodiments will not be repeated for the fifth embodiment. In the fifth embodiment, unless otherwise specified, the same operations as those in the first to fourth embodiments can be performed.

[0144] Fifth Embodiment The semiconductor device manufacturing method of the fifth embodiment differs from the other embodiments mainly in that the semiconductor wafer W is attached to the adhesive layer 22 of the dicing tape 20 with the protective layer 11 disposed between the semiconductor wafer W and the backgrind tape B. More specifically, in the semiconductor device manufacturing method of the fifth embodiment, as shown in FIG. 9A , the protective layer 11 is superimposed on the circuit surface of the semiconductor wafer W, and then the backgrind tape B is superimposed on the protective layer 11. Note that the backgrind tape B may be superimposed on one surface of the protective layer 11 before the semiconductor wafer W is superimposed on the other surface of the protective layer 11, or the semiconductor wafer W may be superimposed on the other surface of the protective layer 11 before the backgrind tape B is superimposed on one surface of the protective layer 11.

[0145] With the semiconductor wafer W, protective layer 11, and backgrinding tape B stacked together, a grinding process is performed on the surface of the semiconductor wafer W on which no circuit components are arranged. Specifically, as shown in Fig. 9A, the semiconductor wafer W is ground using a grinding pad K (backgrinding process) until it reaches a predetermined thickness. The thickness of the semiconductor wafer W is reduced to the predetermined thickness by the grinding process (see Fig. 9B).

[0146] Next, in the mounting step, the ground surface of the semiconductor wafer W (the surface on which no circuit components are arranged) is superimposed on the adhesive layer 22 of the dicing tape 20. At this time, as shown in Fig. 9C, the protective layer 11 is attached to the circuit surface of the semiconductor wafer W, and further, the backgrinding tape B is attached to the protective layer 11.

[0147] After the semiconductor wafer W is superimposed on the adhesive layer 22 of the dicing tape 20, the stealth processing step can be carried out in the same manner as described above. Then, the protective layer 11 attached to the semiconductor wafer W is peeled off from the backgrind tape B, and the backgrind tape B is removed (see FIG. 9D). Note that the stealth processing step may be carried out after the backgrind tape B is removed.

[0148] Thereafter, by using methods similar to those described above, an expanding process for dividing the semiconductor wafer W and the protective layer 11 into small pieces, a removal process for removing the small pieces 11' of the protective layer attached to the semiconductor chip X, a pick-up process for removing the semiconductor chip X, and a bonding process for bonding the semiconductor chip X to an adherend can be carried out.

[0149] Although the manufacturing method of the electronic component device according to the embodiment of the present invention is as exemplified above, the present invention is not limited to the manufacturing method of the electronic component device exemplified above. In other words, various forms used in general manufacturing methods of electronic component devices can be adopted within the scope that does not impair the effects of the present invention.

[0150] For example, as described above, the semiconductor wafer used in the manufacturing method of the present invention may be a semiconductor wafer having circuit surfaces formed on both sides, as described in the first embodiment, or may be a semiconductor wafer having a circuit surface formed on only one side, as described in the other embodiments. In other words, circuit components may be arranged on only one of the two sides of the semiconductor chip produced by the manufacturing method of the present invention, or circuit components may be arranged on both sides.

[0151] The present specification discloses the following: (1) A surface-protecting composition for protecting at least one surface of a substrate, the surface-protecting composition comprising a polymer having a hydrophilic group in its molecule and a compound that generates an acid or a base upon at least one of heating or irradiation with active energy rays. Such a surface-protecting composition can form a protective layer that is relatively easily removed upon contact with a liquid containing water after covering at least one surface of a substrate in an electronic component to be manufactured. (2) The surface-protecting composition according to (1) above, wherein the compound is a compound that generates an acid or a base upon irradiation with active energy rays. (3) The surface-protecting composition according to (1) or (2) above, wherein the hydrophilic group of the polymer is a hydroxy group or a carboxy group. (4) A surface-protecting composition having a water absorption rate of 0.1% by mass or more but less than 1.5% by mass before being heated or before being irradiated with active energy rays, and a water absorption rate after being heated or before being irradiated with active energy rays of 500 mJ / cm using a high-pressure mercury lamp. ２(1) The surface protective composition according to any one of (1) to (3) above, wherein the water absorption rate after irradiation is 1.5 mass % or more. (5) The surface protective composition according to any one of (1) to (4) above, wherein the polymer is polyvinyl alcohol or polyethylene oxide. (6) A surface protective sheet comprising a protective layer formed from the surface protective composition according to any one of (1) to (5) above. (7) The surface protective sheet according to (6) above, further comprising a release liner superposed on at least one surface of the protective layer. (8) A method for manufacturing an electronic component device, comprising: a step of protecting at least one of the surfaces to be protected of a substrate by overlaying a protective layer formed from a surface-protecting composition on the surface to be protected; and a step of removing the protective layer overlaid on the surface to be protected, wherein the surface-protecting composition comprises a polymer having a hydrophilic group in its molecule and a compound that generates an acid or a base upon at least one of heating or irradiation with active energy rays, and the removing step comprises generating the acid or the base from the compound by heating or irradiation with active energy rays to increase the hydrophilicity of the protective layer, and then removing the protective layer by dissolving at least a portion of the protective layer in a liquid containing water. In this method for manufacturing an electronic component device, the protective layer can prevent foreign matter from adhering to at least one surface of the substrate in the manufactured electronic component device, and the protective layer can be subsequently removed relatively easily by contacting the protective layer with a liquid containing water. (9) A method for manufacturing an electronic component device according to (8), wherein a circuit component is disposed on the surface to be protected of the substrate.

[0152] The present invention will now be described in more detail with reference to experimental examples, but the present invention is not limited to these examples.

[0153] A commercially available dicing tape (product name "V-12SR" manufactured by Nitto Denko Corporation) was prepared. Furthermore, a bare silicon wafer (disk-shaped, 50 μm thick and 300 mm in diameter) was used instead of a semiconductor wafer. A surface protection sheet was produced as follows. Specifically, a solvent-containing surface protection composition was applied to one side of a release liner, and the solvent was evaporated to laminate the protective layer and release liner. Furthermore, the release liner was attached to the protective layer, producing a surface protection sheet in which the protective layer was disposed between two release liners.

[0154] Examples 1 to 10, Comparative Example (Preparation of Surface Protection Sheet a) The following polyvinyl alcohol (commercially available) was prepared. This polyvinyl alcohol (PVA) was dissolved in one of the following aqueous alcohol solutions to prepare a PVA solution. The following photoacid generator or photobase generator was added to the prepared PVA solution in the amount shown in Table 1 relative to 100 parts by mass of PVA, and the mixture was mixed. Each PVA solution was applied to release liner a (PET film, thickness 50 μm). Each release liner a had a surface that had been treated with a silicone release agent, and the PVA solution was applied to this surface using an applicator. This was then dried at 110°C for 2 minutes to form a 10 μm-thick protective layer superimposed on one side of release liner a. Release liner b (PET film, thickness 25 μm) was then superimposed on the exposed surface of each protective layer. Each release liner b had a side that had been treated with a silicone release agent, and this side was attached to the protective layer. In this way, each surface protection sheet a sandwiched between two release liners was produced. - Polyvinyl alcohol Saponification degree: 35 (mol%), average polymerization degree: 200 - Alcohol aqueous solution 50% ethanol aqueous solution (Examples 1 to 3, 9, 10, Comparative Example) 60% isopropyl alcohol aqueous solution (Examples 4 to 8) - Photoacid generator Sulfonium salt type Product name "CPI-200K" manufactured by San-Apro Co., Ltd. (Gas phase acidity: 256) Chemical name: diphenyl[4-(phenylsulfanyl)phenyl]sulfonium = trifluorotris(pentafluoroethyl)-λ ５-Phosphanoid [Also known as: Diphenyl[4-(phenylthio)phenyl]sulfonium, trifluorotris(1,1,2,2,2-pentafluoroethyl)phosphate(1-) (1:1)] Sulfonium salt type Product name: "CPI-310FG" Manufactured by San-Apro (Gas phase acidity: 259) Iodonium salt type Product name: "IK-1" Manufactured by San-Apro (Gas phase acidity: 256) Chemical name: (4-isopropylphenyl)(4-tolyl)iodonium = trifluoro[tris(pentafluoroethyl)]-λ ５ -Phosphanide [Also known as: [4-(1-Methylethyl)phenyl](4-methylphenyl)iodonium trifluorotris(1,1,2,2,2-pentafluoroethyl)phosphate(1-) (1:1)] -Photobase generator Product name: "WPBG-266" Manufactured by Fujifilm Corporation Chemical name: 2-(3-Benzoylphenyl)propionic acid 1,2-diisopropyl-3[bis(dimethylamino)methylene]guanidine [Also known as: Benzeneacetic acid, 3-benzoyl-α-methyl-, compd. with N,N,N',N'-tetramethyl-N''-[[(1-methylethyl)amino][(1-methylethyl)imino]methyl]guanidine (1:1)] (Mounting process and protection process) The release liner b was peeled off and removed from the prepared surface protection sheet a, exposing one side of the protection layer. This exposed surface was bonded to a bare silicon wafer (substrate) that was overlapping the dicing tape. The exposed surface of the wafer (the surface opposite to the contact surface with the dicing tape) was bonded to the exposed surface of the protective layer from which the release liner b had been peeled off, so that they were in contact. A Nitto Seiki MV3000 vacuum mounter with a stage temperature of 90°C was used for the bonding. In this way, the dicing tape, bare silicon wafer, and protective layer were stacked in this order. (Removal Process) 500 mJ / cm was applied to the protective layer using a high-pressure mercury lamp. ２The protective layer was then subjected to an irradiation treatment (light irradiation treatment including ultraviolet light) to enhance the hydrophilicity of the protective layer. Subsequently, to remove the protective layer, a cleaning unit (product name DFD6361) manufactured by DISCO Corporation was used to perform the removal process as follows. While rotating a disk-shaped stage supporting the dicing tape from below in the circumferential direction, water at 25°C was sprayed toward the semiconductor chips attached to the small pieces of the die bond sheet. The stage rotation speed was 1000 rpm, and the water spraying time was as shown in Table 1.

[0155] [Comparative Example] Surface protection sheet b was produced in the same manner as in Example 1, except that no photoacid generator was added to the PVA aqueous solution when producing the protective layer of the surface protection sheet, that the fragmented protective layer was not irradiated with ultraviolet light in the removal process, and that the water spray time in the removal process was changed.

[0156] <Water Absorption Rate of Protective Layer Before and After UV Irradiation> The water absorption rate of the protective layer was measured by Karl Fischer coulometric titration using a moisture measuring device (product name "CA-07") and a moisture vaporizer (product name "VA-07") manufactured by Mitsubishi Chemical Analytical Corporation. Specifically, a test sample of the protective layer weighed approximately 4 mg was placed in a steady state of 23°C and 50% RH. The test sample was then heated at 150°C for 3 minutes using the moisture vaporizer to evaporate the moisture in the test sample, while measuring the amount of vaporized moisture. The water absorption rate was calculated from the ratio of the measured moisture amount to the mass of the test sample before heating.

[0157] <Evaluation: Adhesion to Substrate (Before UV Irradiation)> The adhesion of the protective layer to the silicon bare wafer was evaluated according to the following evaluation criteria: (Good) Adhesion strength of the protective layer to the silicon bare wafer was 0.2 N / 100 mm or more (Poor) Adhesion strength of the protective layer to the silicon bare wafer was less than 0.2 N / 100 mm

[0158] <Evaluation: Ease of Removal of Protective Layer (After UV Irradiation)> After the removal step was carried out as described above, the water used to remove the protective layer was removed. Furthermore, the surface of the bare silicon wafer was analyzed with a Fourier transform infrared spectrophotometer (FT-IR). This analysis confirmed the presence or absence of residual organic matter. The evaluation criteria for the ease of removal of the protective layer are as follows: (Good) No residue of the protective layer was found by visual inspection (800 to 4000 cm －１ (fairly good) No residue of the protective layer is visually observed (however, the maximum absorption at 800 to 4000 cm is 0.05 or less) －１ (Poor) Residue of the protective layer is visually observed.

[0159] Each of the manufacturing methods of the Examples and Comparative Examples was carried out as described above. Table 1 shows the details of the protective layer of the surface protection sheet used in each manufacturing method and the evaluation results.

[0160]

[0161] As can be seen from the above evaluation results, by manufacturing a semiconductor device using the semiconductor device manufacturing method of the embodiment, it was possible to prevent foreign matter from adhering to the circuit surface of the semiconductor chip (die), thereby protecting the circuit surface. Furthermore, in the removal process, the multiple small pieces of the protective layer could be removed relatively easily with water, allowing for efficient manufacturing of the semiconductor device. Furthermore, there was no significant difference in the removability of the protective layer whether the amount of energy irradiated to the protective layer in the removal process was high or low (whether the ultraviolet irradiation time was long or short).

[0162] By carrying out the method for manufacturing a semiconductor device according to the embodiment as described above, it is possible to efficiently manufacture a semiconductor device in which a plurality of semiconductor chips are stacked together, with almost no foreign matter adhering thereto.

[0163] The method for manufacturing an electronic component device of the present invention is suitably used for manufacturing a semiconductor device having, for example, a semiconductor integrated circuit.

[0164] 10: Surface protection sheet, 11: Protective layer, 11': Small piece of protective layer, 15: Release liner, 20: Dicing tape, 21: Base layer, 22: Adhesive layer, 30: Die bond sheet, G: Glass carrier, W: Semiconductor wafer, X: Semiconductor chip, V: Through via, D: Electrode portion, B: Backgrinding tape.

Claims

1. A surface protecting composition for protecting at least one surface of a substrate, comprising: The composition comprises a polymer having a hydrophilic group in the molecule and a compound that generates an acid or a base upon at least one of heating and irradiation with active energy rays, the water absorption rate before being heated or before being irradiated with active energy rays is 0.1% by mass or more and less than 1.5% by mass, The surface protecting composition has a water absorption rate of 1.5 mass % or more after being heated or after being irradiated with 500 mJ / cm 2 of active energy rays from a high-pressure mercury lamp.

2. The surface protecting composition according to claim 1 , wherein the compound generates an acid or a base upon irradiation with the active energy rays.

3. 3. The surface protecting composition according to claim 1, wherein the hydrophilic group of the polymer is a hydroxy group or a carboxy group.

4. A surface protection sheet comprising a protective layer formed from the surface protection composition according to claim 1 or 2.

5. The surface protection sheet according to claim 4 , further comprising a release liner superimposed on at least one surface of the protective layer.

6. a step of protecting at least one of the surfaces of the substrate by overlaying a protective layer formed from a surface protection composition on the surface to be protected; removing the protective layer that overlaps the surface to be protected; The surface protecting composition includes a polymer having a hydrophilic group in the molecule and a compound that generates an acid or a base upon at least one of heating and irradiation with active energy rays, In the removing step, the acid or the base is generated from the compound by heating or irradiation with active energy rays to increase the hydrophilicity of the protective layer, and at least a portion of the protective layer is dissolved in a liquid containing water to remove the protective layer. the water absorption of the surface protecting composition before being heated or before being irradiated with active energy rays is 0.1% by mass or more and less than 1.5% by mass; the surface protective composition after being heated or after being irradiated with 500 mJ / cm 2 of active energy rays from a high-pressure mercury lamp has a water absorption rate of 1.5 mass % or more;

7. The method for manufacturing an electronic component device according to claim 6 , wherein a circuit component is disposed on the surface to be protected of the substrate.

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