WO2022201788A1 - 半導体加工用粘着テープおよび半導体装置の製造方法 - Google Patents
半導体加工用粘着テープおよび半導体装置の製造方法 Download PDFInfo
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- WO2022201788A1 WO2022201788A1 PCT/JP2022/001807 JP2022001807W WO2022201788A1 WO 2022201788 A1 WO2022201788 A1 WO 2022201788A1 JP 2022001807 W JP2022001807 W JP 2022001807W WO 2022201788 A1 WO2022201788 A1 WO 2022201788A1
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- WIPO (PCT)
- Prior art keywords
- adhesive tape
- meth
- adhesive
- parts
- semiconductor wafer
- Prior art date
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
Definitions
- the present invention relates to an adhesive tape for semiconductor processing, and more particularly, a method of forming grooves on the surface of a wafer, or forming a modified region inside the wafer with a laser, and singulating the wafer by stress or the like during grinding of the backside of the wafer.
- the present invention relates to an adhesive tape preferably used for temporarily holding a semiconductor wafer or chip when manufacturing a semiconductor device using , and a method of manufacturing a semiconductor device using the adhesive tape.
- DBG Dicing Before Grinding
- LDBG Laser Dicing Before Grinding
- an adhesive tape called a backgrind sheet is placed on the wafer surface to protect the circuits on the wafer surface and to hold the semiconductor wafer and semiconductor chips. is generally attached.
- an adhesive tape having an adhesive layer is attached to the ground surface.
- the adhesive tape attached to the wafer surface is peeled off after its adhesive strength is reduced by irradiation with energy rays such as ultraviolet rays. Through such a process, an adhesive tape is attached to the back surface of the wafer.
- Patent Document 1 proposes a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer that uses a pressure-sensitive adhesive whose tack force decreases by 60% or more after UV irradiation in the presence of oxygen.
- chip crack chipping or breakage of the chip
- FIG. 1 is a schematic diagram showing how the thickness of the semiconductor wafer 20 to which the adhesive tape 10 is attached is gradually reduced when the backside of the semiconductor wafer 20 is ground.
- (1) shows the state before back grinding
- (3) shows the state when the thickness of the semiconductor wafer is about 30 ⁇ m
- (2) shows the state from (1) to (3).
- the semiconductor wafer 20 before grinding has rounded side surfaces.
- the adhesive tape 10 protects the circuits on the surface of the wafer, and usually includes a material that is flat and hard enough to hold the wafer and chips. Therefore, when the adhesive tape 10 is attached to the wafer 20 before grinding, there is a slight area where the adhesive tape does not adhere to the outer edge of the wafer 20, as shown in FIG. 1(1).
- the thickness of the semiconductor wafer 20 decreases and the size changes as the wafer backside grinding progresses through (1), (2), and (3), but the size of the adhesive tape 10 does not change. do not have. Then, when the thickness of the wafer 20 is reduced to about 30 ⁇ m by grinding the back surface of the wafer, the rounded portion of the side surface of the wafer 20 is removed as shown in FIG. 1(3). Then, even if the shape of the adhesive tape is substantially the same as that of the wafer before grinding as shown in FIG. parts are exposed. When the adhesive tape is irradiated with energy rays such as ultraviolet rays in this state, the adhesive strength of the portion of the adhesive tape that is in close contact with the wafer is sufficiently reduced.
- energy rays such as ultraviolet rays
- the oxygen in the atmosphere inhibits the adhesive from curing, and the irradiation of energy rays such as ultraviolet rays can also cause the adhesive to harden.
- the adhesive strength does not decrease sufficiently.
- the adhesive tape has an uncured portion even after being irradiated with energy rays such as ultraviolet rays.
- a dicing die bonding tape is attached as an adhesive tape to the back surface of the wafer after back grinding.
- 2 and 3 are schematic diagrams of a laminated body in which a dicing/die bonding tape 30 is further attached to a semiconductor wafer 20 after back grinding to which an adhesive tape 10 is attached.
- the dicing die bonding tape 30 includes an adhesive layer (not shown) and is attached to the semiconductor wafer 20 by the adhesive layer.
- FIG. 3 shows a state in which a dicing die-bonding tape 30 is attached to a semiconductor wafer 20 whose backside has been ground to an extremely thin thickness of about 30 ⁇ m.
- FIG. 3 shows a state in which a dicing die-bonding tape 30 is attached to a semiconductor wafer 20 whose backside has been ground to an extremely thin thickness of about 30 ⁇ m.
- FIG. 1 shows a state in which a dicing die-bonding tape 30 is attached to a semiconductor wafer 20 whose backside has been ground to an extremely thin thickness of
- FIG. 2 shows a state in which a dicing die bonding tape 30 is attached to a semiconductor wafer 20 and the thickness of the semiconductor wafer 20 is larger than that in FIG.
- the thickness of the semiconductor wafer 20 after back grinding is greater than the thickness of the dicing die bonding tape 30, even if the dicing die bonding tape 30 is attached, the uncured portion of the adhesive tape 10 remains the same as the dicing die bonding tape 30. Do not touch the adhesive layer of the However, as shown in FIG.
- the present invention has been made in view of the above-mentioned prior art, and an object of the present invention is to provide an adhesive tape for semiconductor processing that can suppress chip cracking when the adhesive tape is peeled off.
- the gist of the present invention aimed at solving such problems is as follows.
- An adhesive tape having a substrate and an adhesive layer With one surface of the adhesive layer exposed to the atmosphere, the adhesive tape was irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light amount of 500 mJ/cm 2 .
- the pressure-sensitive adhesive layer contains an acrylic resin
- the pressure-sensitive adhesive layer With one surface of the pressure-sensitive adhesive layer exposed to the atmosphere, the pressure-sensitive adhesive layer is exposed after irradiating the pressure-sensitive adhesive tape with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light intensity of 500 mJ/cm 2 .
- the semiconductor wafer having the adhesive tape attached to the front surface and having the groove or the modified region formed therein is ground from the back side, and separated into a plurality of chips starting from the groove or the modified region. process and peeling off the adhesive tape from the plurality of chips;
- a method of manufacturing a semiconductor device comprising:
- the adhesive strength of the adhesive layer can be sufficiently reduced in an air atmosphere. As a result, the occurrence of cracks in the semiconductor chip can be suppressed.
- FIG. 1 is a schematic diagram showing the progress of backside grinding of a semiconductor wafer.
- FIG. 2 is a schematic diagram of a laminate composed of the adhesive tape 10, the semiconductor wafer 20 after back grinding, and the dicing/die bonding tape 30, and shows the case where the thickness of the semiconductor wafer 20 is greater than that in FIG.
- FIG. 3 is a schematic diagram of a laminated body composed of an adhesive tape 10, a semiconductor wafer 20 after back grinding, and a dicing/die bonding tape 30. The semiconductor wafer 20 is back ground to a very thin thickness of about 30 ⁇ m. Indicates status.
- FIG. 4 is a schematic diagram showing the adhesive tape according to this embodiment.
- FIG. 5 is a schematic diagram of a laminated body composed of the adhesive tape according to the present embodiment, the semiconductor wafer 20 after back grinding, and the dicing die bonding tape 30. Shows if ground.
- Form semiconductor processing means that it can be used in each process such as transportation of semiconductor wafers, back grinding, dicing, and pickup of semiconductor chips.
- the "front surface” of a semiconductor wafer refers to the surface on which circuits are formed, and the “back surface” refers to the surface on which no circuits are formed. Separation of a semiconductor wafer means dividing the semiconductor wafer into individual circuits to obtain semiconductor chips.
- DBG refers to a method in which a groove of a predetermined depth is formed on the front side of the wafer, then the wafer is ground from the back side, and the wafer is singulated by grinding.
- the grooves formed on the surface side of the wafer are formed by a method such as blade dicing, laser dicing or plasma dicing.
- LDBG is a modification of DBG, and refers to a method in which a laser is used to provide a modified region inside the wafer, and the wafer is singulated by stress or the like during grinding of the back surface of the wafer.
- the adhesive tape for semiconductor processing according to the present invention may be simply referred to as "adhesive tape".
- the adhesive tape 100 means a laminate including a substrate 110 and an adhesive layer 120.
- the adhesive tape 100 may have a buffer layer on at least one surface of the substrate 110 .
- a primer layer may be formed on the surface of the substrate on the pressure-sensitive adhesive layer side, and a release sheet may be laminated on the surface of the pressure-sensitive adhesive layer to protect the pressure-sensitive adhesive layer until use.
- the base material may be a single layer or may be a multilayer. The same applies to the adhesive layer and the buffer layer. The configuration of each member of the adhesive tape for semiconductor processing according to this embodiment will be described in more detail below.
- one surface of the adhesive layer is exposed to the atmosphere, and the adhesive tape is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light amount of 500 mJ/cm 2 .
- a PMMA plate is attached to the exposed surface of the adhesive layer at 23° C. and 50% RH under the conditions of one reciprocation with a 2 kg roll, left for 30 minutes, and then the adhesive tape is peeled off at 180°. It is 1600 mN/25 mm or less, preferably 1100 mN/25 mm or less, more preferably 980 mN/25 mm or less, still more preferably 800 mN/25 mm or less.
- the lower limit of the peel strength is not particularly limited, but is usually 50 N/25 mm, preferably 80 N/25 mm.
- the ultraviolet irradiation is performed from the base material side.
- PMMA is polymethyl methacrylate
- the PMMA plate "Acrylite L001" manufactured by Mitsubishi Chemical Co., Ltd. having a thickness of 2 mm, a width of 70 mm, and a length of 150 mm is used.
- the above-mentioned peel strength is measured under the conditions that the width of the adhesive tape is 25 mm, the peel speed is 300 mm/min, and the measurement temperature is 25°C.
- the peel strength is adjusted so that the pressure-sensitive adhesive layer contains an acrylic resin, and further, by adjusting the amount of polymerized units derived from 2-hydroxyethyl methacrylate (hereinafter sometimes abbreviated as HEMA), You can control it.
- HEMA 2-hydroxyethyl methacrylate
- the peel strength can be controlled within the above range by preparing the pressure-sensitive adhesive layer so that the content of polymerized units derived from HEMA is 6 parts by mass or more with respect to 100 parts by mass of the total acrylic resin.
- the pressure-sensitive adhesive layer is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light intensity of 500 mJ/cm 2 with one surface of the pressure-sensitive adhesive layer exposed to the atmosphere.
- the surface free energy of the exposed surface of is preferably less than 36 mJ/m 2 , more preferably 32 mJ/m 2 or less, and preferably 30 mJ/m 2 or less. From the viewpoint of sufficiently reducing the adhesive strength of the pressure-sensitive adhesive layer, the surface free energy is preferably within the above range.
- the lower limit of the surface free energy is not particularly limited, it is usually 18 mJ/m 2 , preferably 22 mJ/m 2 .
- the ultraviolet irradiation is performed from the substrate side. Further, the surface free energy is determined by the Kitazaki-Hata method based on the contact angle (measurement temperature: 25° C.) of various droplets measured. Specifically, diiodomethane, 1-bromonaphthalene, and distilled water are used as droplets, and the contact angle (measurement temperature: 25° C.) is measured by the sessile droplet method in accordance with JIS R 3257:1999. Surface free energy (mJ/m 2 ) is determined by the Kitazaki-Hata method based on the value of the contact angle.
- the above surface free energy can be controlled by preparing the pressure-sensitive adhesive layer so that it contains an acrylic resin, and further by adjusting the amount of polymerized units derived from HEMA.
- the surface free energy can be controlled within the above range by preparing the pressure-sensitive adhesive layer so that the content of polymerized units derived from HEMA is 6 parts by mass or more with respect to 100 parts by mass of the total acrylic resin.
- the The surface elastic modulus of the exposed surface of the pressure-sensitive adhesive layer is preferably 5 MPa or higher, more preferably 6 MPa or higher, and still more preferably 6.5 MPa or higher. From the viewpoint of sufficiently reducing the adhesive strength of the pressure-sensitive adhesive layer, the surface elastic modulus is preferably within the above range. Although the upper limit of the surface elastic modulus is not particularly limited, it is usually 17 MPa, preferably 14 MPa.
- the ultraviolet irradiation is performed from the base material side.
- the surface elastic modulus is measured using an atomic force microscope. Specifically, a silicon nitride cantilever (tip radius: 2 nm, resonance frequency: 70 kHz, spring constant: 0.4 N/m) installed in an atomic force microscope was used to irradiate the surface of the adhesive layer at room temperature. Pushing is performed at a pushing amount of 5 nm and a scanning speed of 5 Hz, followed by pulling apart.
- the surface elastic modulus is calculated by fitting the obtained force curve curve (horizontal axis is sample deformation amount, vertical axis is measurement load) with JKR theoretical formula. Let the average value of the value obtained by measuring 4096 points in 5 micrometers x 5 micrometers on the surface of an adhesive layer be a surface elastic modulus (MPa).
- the surface elastic modulus can be controlled by preparing the pressure-sensitive adhesive layer so that it contains an acrylic resin, and by adjusting the amount of polymerized units derived from HEMA.
- the surface elastic modulus can be controlled within the above range by preparing the pressure-sensitive adhesive layer so that the content of polymerized units derived from HEMA is 6 parts by mass or more with respect to 100 parts by mass of the total acrylic resin.
- the adhesive tape with one surface of the adhesive layer exposed to the atmosphere, the adhesive tape is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light amount of 500 mJ/cm 2 .
- the adhesion energy of the exposed surface of the pressure-sensitive adhesive layer is preferably 0.220 J/m 2 or less, more preferably 0.200 J/m 2 or less, and still more preferably 0.190 J/m 2 or less.
- the cohesion energy is preferably within the above range.
- the lower limit of the adhesion energy is not particularly limited, it is usually 0.12 J/m 2 , preferably 0.14 J/m 2 .
- the ultraviolet irradiation is performed from the substrate side.
- the adhesion energy is measured using an atomic force microscope. Specifically, a silicon nitride cantilever (tip radius: 2 nm, resonance frequency: 70 kHz, spring constant: 0.4 N/m) installed in an atomic force microscope was used to irradiate the surface of the adhesive layer at room temperature. Pushing is performed at a pushing amount of 5 nm and a scanning speed of 5 Hz, followed by pulling apart. The obtained force curve (horizontal axis is the sample deformation amount and vertical axis is the measured load) is fitted with the JKR theoretical formula to calculate the adhesion energy. Let the average value of the value obtained by measuring 4096 points in 5 micrometers x 5 micrometers on the surface of an adhesive layer be adhesion energy (J/m ⁇ 2 >).
- the above cohesion energy can be controlled by preparing the pressure-sensitive adhesive layer so that it contains an acrylic resin, and by adjusting the amount of polymerized units derived from HEMA.
- the adhesion energy can be controlled within the above range by preparing the pressure-sensitive adhesive layer so that the content of polymerized units derived from HEMA is 6 parts by mass or more with respect to 100 parts by mass of the total amount of the acrylic resin.
- the thickness of the adhesive layer is not particularly limited as long as the adhesive layer has a peel strength of 1600 mN/25 mm or less after ultraviolet irradiation in a state of being exposed to the atmosphere as described above, but is preferably less than 100 ⁇ m, It is more preferably 5 to 80 ⁇ m, still more preferably 10 to 70 ⁇ m.
- the adhesive layer is not particularly limited as long as the peel strength after ultraviolet irradiation is 1600 mN/25 mm or less in a state exposed to the atmosphere as described above, but it is preferably formed from an acrylic adhesive. Moreover, the adhesive layer is preferably formed from an energy ray-curable adhesive.
- energy ray refers to ultraviolet rays, electron beams, etc., and preferably ultraviolet rays are used.
- an energy ray-curable adhesive for forming the adhesive layer for example, in addition to a non-energy ray-curable adhesive resin (also referred to as “adhesive resin I”), an energy ray-curable compound other than the adhesive resin can be used.
- An energy ray-curable pressure-sensitive adhesive composition (hereinafter also referred to as “X-type pressure-sensitive adhesive composition”) can be used.
- an energy ray-curable adhesive resin hereinafter also referred to as “adhesive resin II" obtained by introducing an unsaturated group into the side chain of a non-energy ray-curable adhesive resin is used.
- a pressure-sensitive adhesive composition (hereinafter, also referred to as "Y-type pressure-sensitive adhesive composition”) containing as a main component and not containing an energy ray-curable compound other than the pressure-sensitive adhesive resin may also be used.
- the energy ray-curable adhesive a combined type of X-type and Y-type, that is, in addition to the energy ray-curable adhesive resin II, an energy ray-curable adhesive containing an energy ray-curable compound other than the adhesive resin is used.
- An adhesive composition (hereinafter also referred to as "XY type adhesive composition") may be used. Among these, it is preferable to use the XY type adhesive composition. By using the XY type, it is possible to have sufficient adhesive properties before curing, while sufficiently reducing the peel strength to the semiconductor wafer after curing.
- the adhesive may be formed from a non-energy ray-curable adhesive composition that does not cure even when irradiated with energy rays.
- the non-energy ray-curable adhesive composition contains at least the non-energy ray-curable adhesive resin I, but does not contain the energy ray-curable adhesive resin II and the energy ray-curable compound. be.
- adhesive resin is used as a term indicating one or both of the above-described adhesive resin I and adhesive resin II.
- specific adhesive resins include acrylic resins, urethane resins, rubber resins, and silicone resins, with acrylic resins being preferred.
- the acrylic pressure-sensitive adhesive in which an acrylic resin is used as the pressure-sensitive adhesive resin will be described in more detail below.
- Acrylic polymer is used for acrylic resin.
- the acrylic polymer is obtained by polymerizing a monomer containing at least an alkyl (meth)acrylate, and contains structural units derived from the alkyl (meth)acrylate.
- Alkyl (meth)acrylates include those having 1 to 20 carbon atoms in the alkyl group, and the alkyl group may be linear or branched.
- alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ) acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate and the like. You may use an alkyl (meth)acrylate individually or in combination of 2 or more types.
- the acrylic polymer preferably contains a structural unit derived from an alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms.
- the number of carbon atoms in the alkyl (meth)acrylate is preferably 4-12, more preferably 4-6.
- the alkyl (meth)acrylate having an alkyl group having 4 or more carbon atoms is preferably an alkyl acrylate.
- an alkyl group having a carbon number of 4 or more is added in order to adjust the elastic modulus and adhesive properties of the pressure-sensitive adhesive layer.
- a copolymer containing 1 to 3 alkyl (meth)acrylate-derived structural units is preferred.
- the alkyl (meth)acrylate is preferably an alkyl (meth)acrylate having 1 or 2 carbon atoms, more preferably methyl (meth)acrylate, and most preferably methyl methacrylate.
- the content of the alkyl (meth)acrylate having 1 to 3 carbon atoms in the alkyl group is preferably 1 to 30 parts by mass, more preferably 3 to 26 parts by mass, with respect to 100 parts by mass of the total amount of the monomer. parts by mass, more preferably 5 to 22 parts by mass.
- the acrylic polymer preferably has structural units derived from a functional group-containing monomer in addition to the structural units derived from the alkyl (meth)acrylate described above.
- the functional group of the functional group-containing monomer includes a hydroxyl group, a carboxyl group, an amino group, an epoxy group and the like.
- the functional group-containing monomer reacts with a cross-linking agent described later to become a cross-linking starting point, or reacts with an unsaturated group-containing compound to introduce an unsaturated group into the side chain of the acrylic polymer. be.
- Functional group-containing monomers include hydroxyl group-containing monomers, carboxy group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and the like. In this embodiment, it is particularly preferable to use HEMA in a predetermined amount or more as the functional group-containing monomer.
- the pressure-sensitive adhesive layer preferably contains an acrylic resin, and the content of polymerized units derived from HEMA is preferably 6 parts by mass or more with respect to 100 parts by mass of the total acrylic resin. .
- the content of polymerized units derived from HEMA may be 10 parts by mass or more, or 12 parts by mass or more.
- the content of polymerized units derived from HEMA is used within the above range, so that the peel strength, surface free energy, surface elastic modulus, and cohesion energy of the pressure-sensitive adhesive are within the desired ranges. can do.
- the upper limit of the content of polymerized units derived from HEMA in the pressure-sensitive adhesive layer is not particularly limited, but it is usually 35 parts by mass, preferably 32 parts by mass with respect to 100 parts by mass of the acrylic resin.
- hydroxyl group-containing monomers other than HEMA carboxy group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, and the like may be used alone or in combination of two or more.
- hydroxyl group-containing monomers and carboxy group-containing monomers are preferably used, and hydroxyl group-containing monomers are more preferably used.
- hydroxyl group-containing monomers other than HEMA described above examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3- Hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol;
- Carboxy group-containing monomers include, for example, ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and their anhydrides , 2-carboxyethyl methacrylate and the like.
- monocarboxylic acids such as (meth)acrylic acid and crotonic acid
- dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and their anhydrides
- 2-carboxyethyl methacrylate and the like include, for example, ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic
- the content of functional group-containing monomers other than HEMA is preferably 1 to 35 parts by mass, more preferably 3 to 32 parts by mass, and still more preferably 6 to 35 parts by mass, based on 100 parts by mass of the total amount of monomers constituting the acrylic polymer. 30 parts by mass.
- the acrylic polymer may contain structural units derived from monomers copolymerizable with the above acrylic monomers, such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide. may contain.
- the above acrylic polymer can be used as a non-energy ray-curable adhesive resin I (acrylic resin).
- the energy ray-curable acrylic resin include those obtained by reacting the functional group of the acrylic polymer I with a compound having a photopolymerizable unsaturated group (also referred to as an unsaturated group-containing compound). .
- the unsaturated group-containing compound is a compound having both a substituent capable of bonding to the functional group of the acrylic polymer and a photopolymerizable unsaturated group.
- the photopolymerizable unsaturated group includes a (meth)acryloyl group, a vinyl group, an allyl group, a vinylbenzyl group, etc., and a (meth)acryloyl group is preferred.
- an isocyanate group, a glycidyl group, etc. are mentioned as a functional group and a bondable substituent which the unsaturated group containing compound has.
- examples of unsaturated group-containing compounds include (meth)acryloyloxyethyl isocyanate, (meth)acryloylisocyanate, glycidyl (meth)acrylate, and the like.
- the unsaturated group-containing compound preferably reacts with a part of the functional groups of the acrylic polymer.
- 50 to 98 mol% of the functional groups of the acrylic polymer include It is preferable to react the contained compounds, more preferably 55 to 93 mol %.
- the weight average molecular weight (Mw) of the acrylic resin is preferably 300,000 to 1,600,000, more preferably 400,000 to 1,400,000, and still more preferably 500,000 to 1,200,000.
- Energy ray-curable compound contained in the X-type or XY-type pressure-sensitive adhesive composition, a monomer or oligomer having an unsaturated group in the molecule and capable of being polymerized and cured by energy ray irradiation is preferable.
- energy ray-curable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4- Polyvalent (meth)acrylate monomers such as butylene glycol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, epoxy ( Oligomers such as meth)acrylates can be mentioned.
- urethane (meth)acrylate oligomers are preferred because they have relatively high molecular weights and are unlikely to reduce the shear storage modulus of the pressure-sensitive adhesive layer.
- the energy ray-curable compound has a molecular weight (weight average molecular weight in the case of an oligomer) of preferably 100 to 12,000, more preferably 200 to 10,000, still more preferably 400 to 8,000, and particularly preferably 600 to 6,000.
- the content of the energy ray-curable compound in the X-type adhesive composition is preferably 40 to 200 parts by mass, more preferably 50 to 150 parts by mass, and still more preferably 60 to 100 parts by mass with respect to 100 parts by mass of the adhesive resin. 90 parts by mass.
- the content of the energy ray-curable compound in the XY-type adhesive composition is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 100 parts by mass of the adhesive resin. is 3 to 15 parts by mass.
- the adhesive resin is energy ray-curable, even if the content of the energy ray-curable compound is small, it is possible to sufficiently reduce the peel strength after energy ray irradiation. is.
- the pressure-sensitive adhesive composition preferably further contains a cross-linking agent.
- the cross-linking agent reacts with, for example, a functional group derived from a functional group-containing monomer possessed by the adhesive resin to cross-link the adhesive resins.
- cross-linking agents examples include isocyanate-based cross-linking agents such as tolylene diisocyanate, hexamethylene diisocyanate, and adducts thereof; epoxy-based cross-linking agents such as ethylene glycol glycidyl ether; hexa[1-(2-methyl)-aziridinyl ] aziridine-based cross-linking agents such as triphosphatriazine; chelate-based cross-linking agents such as aluminum chelate; These cross-linking agents may be used alone or in combination of two or more.
- isocyanate-based cross-linking agents are preferable from the viewpoints of increasing cohesive strength and improving adhesive strength, and from the viewpoints of availability and the like.
- the amount of the cross-linking agent is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the adhesive resin. 0.05 to 4 parts by mass.
- the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition is energy ray-curable, the pressure-sensitive adhesive composition preferably further contains a photopolymerization initiator.
- a photopolymerization initiator By including a photopolymerization initiator, the curing reaction of the pressure-sensitive adhesive composition can sufficiently proceed even with relatively low-energy energy rays such as ultraviolet rays.
- photopolymerization initiators examples include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and photosensitizers such as amines and quinones.
- the amount of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the adhesive resin. is.
- the adhesive composition may contain other additives as long as the effects of the present invention are not impaired.
- Other additives include, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, and the like.
- the blending amount of the additives is preferably 0.01 to 6 parts by mass with respect to 100 parts by mass of the adhesive resin.
- the adhesive composition may be further diluted with an organic solvent to form a solution of the adhesive composition, from the viewpoint of improving coatability to the base material, buffer layer and release sheet.
- organic solvents include methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol and isopropanol.
- the organic solvents used during the synthesis of the adhesive resin may be used as they are. may be added with one or more organic solvents.
- the substrate preferably has a Young's modulus of 1000 MPa or more at 23°C. If a base material with a Young's modulus of less than 1000 MPa is used, the holding performance of the adhesive tape on the semiconductor wafer or semiconductor chip is reduced, and vibrations, etc. during back grinding cannot be suppressed, resulting in chipping or breakage of the semiconductor chip. easier. On the other hand, by setting the Young's modulus of the base material to 1000 MPa or more at 23° C., the performance of holding the semiconductor wafer or semiconductor chip by the adhesive tape is enhanced, suppressing vibration during back grinding, etc., and preventing chipping and breakage of the semiconductor chip. can.
- the Young's modulus of the substrate at 23° C. is more preferably 1800 to 30000 MPa, still more preferably 2500 to 6000 MPa.
- the thickness of the substrate is not particularly limited, it is preferably 110 ⁇ m or less, more preferably 15 to 110 ⁇ m, even more preferably 20 to 105 ⁇ m. By setting the thickness of the substrate to 110 ⁇ m or less, it becomes easier to control the peel strength of the adhesive tape. In addition, when the thickness is 15 ⁇ m or more, the base material can easily function as a support for the adhesive tape.
- the material of the substrate is not particularly limited as long as it satisfies the physical properties described above, and various resin films can be used.
- a base material having a Young's modulus of 1000 MPa or more at 23° C. for example, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyesters such as wholly aromatic polyesters, polyimides, polyamides, polycarbonates, polyacetals, modified polyphenylene oxides, and polyphenylene sulfides. , polysulfone, polyetherketone, and biaxially oriented polypropylene.
- a film containing one or more selected from a polyester film, a polyamide film, a polyimide film, and a biaxially stretched polypropylene film is preferable, more preferably a polyester film, and further preferably a polyethylene terephthalate film.
- the substrate may contain plasticizers, lubricants, infrared absorbers, ultraviolet absorbers, fillers, colorants, antistatic agents, antioxidants, catalysts, etc., as long as they do not impair the effects of the present invention. good.
- the substrate may be transparent or opaque, and may be colored or vapor-deposited as desired.
- At least one surface of the base material may be subjected to adhesion treatment such as corona treatment in order to improve adhesion to at least one of the buffer layer and the pressure-sensitive adhesive layer.
- the base material may have the resin film described above and an easy-adhesion layer coated on at least one surface of the resin film.
- the easy-adhesion layer-forming composition for forming the easy-adhesion layer is not particularly limited, but examples thereof include compositions containing polyester-based resins, urethane-based resins, polyester-urethane-based resins, acrylic-based resins, and the like.
- the easily adhesive layer-forming composition may optionally contain a cross-linking agent, a photopolymerization initiator, an antioxidant, a softening agent (plasticizer), a filler, an antirust agent, a pigment, a dye, and the like. good.
- the thickness of the easy-adhesion layer is preferably 0.01 to 10 ⁇ m, more preferably 0.03 to 5 ⁇ m.
- the thickness of the easy-adhesion layer in the examples of the present application is smaller than the thickness of the substrate, the thickness of the resin film having the easy-adhesion layer and the thickness of the substrate are substantially the same.
- the material of the easy-adhesion layer is soft, it has little effect on the Young's modulus, and the Young's modulus of the substrate is substantially the same as that of the resin film even when the easy-adhesion layer is provided.
- the Young's modulus of the base material can be controlled by selecting the resin composition, adding a plasticizer, and stretching conditions during resin film production. Specifically, when a polyethylene terephthalate film is used as the substrate, the Young's modulus of the substrate tends to decrease as the content of the ethylene component in the copolymer component increases. Moreover, when the amount of the plasticizer blended with respect to the resin composition constituting the base material is increased, the Young's modulus of the base material tends to decrease.
- the adhesive tape according to the present embodiment may have a buffer layer.
- the buffer layer can be provided on at least one side of the substrate, and can also be provided on both sides of the substrate.
- a pressure-sensitive adhesive layer may be provided on one side of the substrate, and a buffer layer may be provided on the other side of the substrate.
- the buffer layer relieves the stress during grinding of the back surface of the semiconductor wafer and prevents the semiconductor wafer from cracking and chipping.
- the buffer layer is a soft layer compared to the base material. Therefore, the Young's modulus of the buffer layer at 23°C is less than the Young's modulus of the substrate at 23°C. Specifically, the Young's modulus of the buffer layer at 23° C. is preferably less than 1000 MPa, more preferably 700 MPa or less, still more preferably 500 MPa or less.
- the thickness of the buffer layer is preferably 1-100 ⁇ m, more preferably 5-80 ⁇ m, and even more preferably 10-60 ⁇ m. By setting the thickness of the buffer layer within the above range, the buffer layer can appropriately relax the stress during back grinding.
- the buffer layer is preferably a cured product of a composition for forming a buffer layer containing an energy ray-polymerizable compound. Further, it may be a layer containing a polyolefin resin film, or a layer containing polyether as a main component.
- a component contained in the layer formed from the buffer layer-forming composition containing the energy ray-polymerizable compound and each component contained in the layer containing the polyolefin resin film will be described in order.
- a composition for forming a buffer layer containing an energy ray-polymerizable compound can be cured by being irradiated with an energy ray.
- the composition for forming a buffer layer containing the energy ray-polymerizable compound more specifically contains the urethane (meth)acrylate (a1).
- the composition for forming a buffer layer includes a polymerizable compound (a2) having an alicyclic or heterocyclic group having 6 to 20 ring atoms and/or a polymerizable compound having a functional group. It is more preferable to contain compound (a3).
- the composition for forming a buffer layer may contain a polyfunctional polymerizable compound (a4).
- the composition for forming a buffer layer preferably contains a photopolymerization initiator, and may contain other additives and resin components within a range that does not impair the effects of the present invention.
- a photopolymerization initiator e.g., a photopolymerization initiator
- each component contained in the buffer layer-forming composition containing the energy ray-polymerizable compound will be described in detail below.
- the urethane (meth)acrylate (a1) is a compound having at least a (meth)acryloyl group and a urethane bond, and has the property of being polymerized and cured by energy ray irradiation.
- Urethane (meth)acrylates (a1) are oligomers or polymers.
- the weight average molecular weight (Mw) of component (a1) is preferably 1,000 to 100,000, more preferably 2,000 to 60,000, still more preferably 10,000 to 30,000.
- the number of (meth)acryloyl groups (hereinafter also referred to as "number of functional groups") in component (a1) may be monofunctional, difunctional, or trifunctional or more, but monofunctional or difunctional is preferred.
- Component (a1) can be obtained, for example, by reacting a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound and a polyvalent isocyanate compound with a (meth)acrylate having a hydroxyl group. In addition, you may use a component (a1) individually or in combination of 2 or more types.
- the polyol compound used as the raw material of component (a1) is not particularly limited as long as it is a compound having two or more hydroxy groups.
- Specific polyol compounds include, for example, alkylene diols, polyether polyols, polyester polyols, and polycarbonate polyols. Among these, polyester-type polyols and polycarbonate-type polyols are preferred.
- the polyol compound may be a difunctional diol, a trifunctional triol, or a tetrafunctional or higher polyol, preferably a bifunctional diol, more preferably a polyester diol or a polycarbonate diol.
- polyvalent isocyanate compounds include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Alicyclic diisocyanates such as ,4'-diisocyanate, ⁇ , ⁇ '-diisocyanatedimethylcyclohexane;4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene- aromatic diisocyanates such as 1,5-diisocyanate; Among these, isophorone diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are preferred.
- a urethane (meth)acrylate (a1) can be obtained by reacting a (meth)acrylate having a hydroxyl group with a terminal isocyanate urethane prepolymer obtained by reacting the above-mentioned polyol compound and a polyvalent isocyanate compound.
- the (meth)acrylate having a hydroxy group is not particularly limited as long as it is a compound having a hydroxy group and a (meth)acryloyl group in at least one molecule.
- Specific (meth)acrylates having a hydroxy group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxycyclohexyl (meth) Acrylate, 5-hydroxycyclooctyl (meth)acrylate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.
- hydroxyalkyl (meth)acrylate hydroxy group-containing (meth)acrylamide such as N-methylol (meth)acrylamide
- hydroxyalkyl (meth)acrylates are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.
- the conditions for reacting the isocyanate-terminated urethane prepolymer and the (meth)acrylate having a hydroxy group are preferably conditions for reacting at 60 to 100° C. for 1 to 4 hours in the presence of a solvent and a catalyst added as necessary.
- the content of component (a1) in the buffer layer-forming composition is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, relative to the total amount (100 parts by mass) of the buffer layer-forming composition. is.
- Component (a2) is a polymerizable compound having an alicyclic or heterocyclic group having 6 to 20 ring atoms, and more preferably a compound having at least one (meth)acryloyl group. Compounds having one (meth)acryloyl group are preferred.
- component (a2) overlaps with the definition of component (a3) described later, the overlapping part is included in component (a3).
- a compound having at least one (meth)acryloyl group, an alicyclic or heterocyclic group having 6 to 20 ring-forming atoms, and a functional group such as a hydroxyl group, an epoxy group, an amide group, or an amino group is a component
- the compound is included in component (a3).
- the number of ring-forming atoms in the alicyclic group or heterocyclic group of component (a2) is preferably 6 to 20, more preferably 6 to 18, still more preferably 6 to 16, particularly preferably 7 to 12. be.
- Atoms forming the ring structure of the heterocyclic group include, for example, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and the like.
- the number of ring-forming atoms refers to the number of atoms constituting the ring itself of a compound having a structure in which atoms are cyclically bonded, and atoms that do not constitute a ring (for example, hydrogen atoms bonded to atoms that constitute a ring). Also, when the ring is substituted with a substituent, the atoms included in the substituent are not included in the number of ring-forming atoms.
- component (a2) examples include isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxy (meth)acrylate, cyclohexyl (meth)acrylate, alicyclic group-containing (meth)acrylates such as adamantane (meth)acrylate; heterocyclic group-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and morpholine (meth)acrylate; and the like.
- alicyclic group-containing (meth)acrylates isobornyl (meth)acrylate is preferred, and among heterocyclic group-containing (meth)acrylates, tetrahydrofurfuryl (meth)acrylate is preferred.
- the content of the component (a2) in the buffer layer-forming composition is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, relative to the total amount (100 parts by mass) of the buffer layer-forming composition. is.
- Component (a3) is a polymerizable compound containing a functional group such as a hydroxyl group, an epoxy group, an amide group, or an amino group, and is preferably a compound having at least one (meth)acryloyl group. Compounds having one (meth)acryloyl group are preferred.
- the component (a3) has good compatibility with the component (a1), and it becomes easy to adjust the viscosity of the composition for forming a buffer layer within an appropriate range. Moreover, even if the buffer layer is made relatively thin, the buffer performance is improved. Examples of component (a3) include hydroxyl group-containing (meth)acrylates, epoxy group-containing compounds, amide group-containing compounds, and amino group-containing (meth)acrylates.
- hydroxyl group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxy Butyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, phenylhydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate and the like.
- epoxy group-containing compounds include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether, and the like.
- epoxy groups such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate Group-containing (meth)acrylates are preferred.
- amide group-containing compounds include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N -Methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide and the like.
- amino group-containing (meth)acrylates include primary amino group-containing (meth)acrylates, secondary amino group-containing (meth)acrylates, and tertiary amino group-containing (meth)acrylates.
- hydroxyl group-containing (meth)acrylates are preferable, and hydroxyl group-containing (meth)acrylates having an aromatic ring such as phenylhydroxypropyl (meth)acrylate are more preferable.
- the content of the component (a3) in the buffer layer-forming composition is, in order to improve the film-forming properties of the buffer layer-forming composition, the total amount (100 parts by mass) of the buffer layer-forming composition: It is preferably 5 to 40 parts by mass, more preferably 7 to 35 parts by mass, still more preferably 10 to 30 parts by mass.
- the content ratio [(a2)/(a3)] of the component (a2) and the component (a3) in the buffer layer-forming composition is preferably 0.5 to 3.0, more preferably 1.0. 0 to 3.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.8.
- a polyfunctional polymerizable compound refers to a compound having two or more photopolymerizable unsaturated groups.
- a photopolymerizable unsaturated group is a functional group containing a carbon-carbon double bond, and examples thereof include (meth)acryloyl group, vinyl group, allyl group, vinylbenzyl group and the like. Two or more photopolymerizable unsaturated groups may be combined.
- a three-dimensional network structure (crosslinked structure) is formed.
- the number of crosslinked structures formed by energy ray irradiation tends to increase, compared to when a compound containing only one photopolymerizable unsaturated group is used.
- component (a4) overlaps with the definitions of components (a2) and (a3) described above, the overlap is included in component (a4).
- a compound having an alicyclic or heterocyclic group with 6 to 20 ring atoms and two or more (meth)acryloyl groups is included in the definition of both component (a4) and component (a2).
- the compound is included in component (a4).
- compounds containing functional groups such as hydroxyl groups, epoxy groups, amide groups and amino groups and having two or more (meth)acryloyl groups are included in the definition of both component (a4) and component (a3).
- the compound is included in component (a4).
- the number of photopolymerizable unsaturated groups (number of functional groups) in the polyfunctional polymerizable compound is preferably 2-10, more preferably 3-6.
- the weight average molecular weight of component (a4) is preferably 30-40,000, more preferably 100-10,000, and even more preferably 200-1,000.
- Examples of specific component (a4) include diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexane.
- the content of the component (a4) in the buffer layer-forming composition is preferably 2 to 40 parts by mass, more preferably 3 to 20 parts by mass, relative to the total amount (100 parts by mass) of the buffer layer-forming composition. , more preferably 5 to 15 parts by mass.
- the composition for forming a buffer layer may contain a polymerizable compound (a5) other than the components (a1) to (a4) as long as the effects of the present invention are not impaired.
- component (a5) include alkyl (meth)acrylates having an alkyl group having 1 to 20 carbon atoms; styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, N-vinylcaprolactam, and the like. vinyl compound of: and the like.
- the content of the component (a5) in the buffer layer-forming composition is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, relative to the total amount (100 parts by mass) of the buffer layer-forming composition. , more preferably 0 to 5 parts by mass, particularly preferably 0 to 2 parts by mass.
- the buffer layer-forming composition preferably further contains a photopolymerization initiator from the viewpoint of shortening the polymerization time by light irradiation and reducing the amount of light irradiation when forming the buffer layer.
- photopolymerization initiators examples include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, peroxide compounds, and photosensitizers such as amines and quinones.
- 1-hydroxycyclohexylphenyl ketone 2-hydroxy-2-methyl-1-phenyl-propan-1-one
- benzoin benzoin methyl ether
- benzoin ethyl ether benzoin isopropyl ether
- benzylphenyl sulfide tetramethylthiuram monosulfide
- azobisisobutyrolnitrile dibenzyl, diacetyl, 8-chloroanthraquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and the like.
- photopolymerization initiators can be used alone or in combination of two or more.
- the content of the photopolymerization initiator in the buffer layer-forming composition is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the total amount of the energy ray-polymerizable compound. parts by mass, more preferably 0.3 to 5 parts by mass.
- the buffer layer-forming composition may contain other additives as long as the effects of the present invention are not impaired.
- Other additives include, for example, antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, and the like.
- the content of each additive in the buffer layer-forming composition is preferably 0.01 to 6 parts by mass with respect to 100 parts by mass of the total amount of the energy ray-polymerizable compound. More preferably, it is 0.1 to 3 parts by mass.
- the buffer layer-forming composition may contain a resin component as long as the effects of the present invention are not impaired.
- the resin component include polyene/thiol-based resins, polyolefin-based resins such as polybutene, polybutadiene, and polymethylpentene, and thermoplastic resins such as styrene-based copolymers.
- the content of these resin components in the buffer layer-forming composition is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, relative to the total amount (100 parts by mass) of the buffer layer-forming composition. , more preferably 0 to 5 parts by mass, particularly preferably 0 to 2 parts by mass.
- the buffer layer formed from the composition for forming a buffer layer containing an energy ray-polymerizable compound is obtained by polymerizing and curing the composition for forming a buffer layer having the above composition by irradiation with an energy ray. That is, the buffer layer is a cured product of the composition for forming a buffer layer. Therefore, the buffer layer contains polymerized units derived from component (a1). Moreover, the buffer layer preferably contains polymerized units derived from the component (a2) and/or polymerized units derived from the component (a3). Furthermore, polymerized units derived from component (a4) and/or polymerized units derived from component (a5) may be contained.
- the content ratio of each polymer unit in the buffer layer usually corresponds to the ratio (feed ratio) of each component constituting the buffer layer-forming composition.
- the buffer layer contains component (a1). It contains 10 to 70 parts by mass of the derived polymerized units.
- the buffer layer It contains 10 to 80 parts by mass of the derived polymerized units. The same applies to components (a3) to (a5).
- the buffer layer may be formed of a layer containing a polyolefin resin film.
- the stress relaxation property may be lower than when the buffer layer is a layer formed from a buffer layer-forming composition containing an energy ray-polymerizable compound.
- the pressure-sensitive adhesive tape having a buffer layer formed of a layer containing a polyolefin resin film on one side of the substrate may warp.
- the buffer layer formed of the layer containing the polyolefin resin film may be provided on at least one side of the substrate, but from the viewpoint of preventing such problems, the buffer layer formed of the layer containing the polyolefin resin film is used. are preferably provided on both sides of the substrate.
- the polyolefin resin is not particularly limited . less than), medium density polyethylene (MDPE, density: 930 kg/m 3 or more, less than 942 kg/m 3 ), high density polyethylene (HDPE, density: 942 kg/m 3 or more), polypropylene resin, polyethylene-polypropylene Polymer, olefin elastomer (TPO), cycloolefin resin, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-maleic anhydride copolymer, ethylene-(meth)acrylic acid copolymer, ethylene- Examples thereof include (meth)acrylic acid ester copolymers and ethylene-(meth)acrylic acid ester-maleic anhydride copolymers. These polyolefin resins can be used alone or in combination of two or more.
- polyethylene resins are preferable, and low-density polyethylene is more preferable, from the viewpoint of obtaining a buffer layer having specific physical properties.
- the buffer layer described above contains additives such as plasticizers, lubricants, infrared absorbers, ultraviolet absorbers, fillers, colorants, antistatic agents, antioxidants, and catalysts, as long as they do not impair the effects of the present invention. You may let Moreover, the buffer layer described above may be transparent or opaque, and may be colored or vapor-deposited as desired.
- a release sheet may be attached to the surface of the adhesive tape.
- the release sheet is attached to the surface of the adhesive layer of the adhesive tape.
- the release sheet is attached to the surface of the adhesive layer to protect the adhesive layer during transportation and storage.
- the release sheet is releasably attached to the adhesive tape, and is peeled off and removed from the adhesive tape before the adhesive tape is used (that is, before wafer attachment).
- a release sheet having at least one surface subjected to a release treatment is used, and specific examples include a release sheet base material coated with a release agent on the surface thereof.
- a resin film is preferable, and as the resin constituting the resin film, for example, polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc. and the like polyolefin resins.
- polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polypropylene resin, polyethylene resin, etc. and the like polyolefin resins.
- release agents include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and the like.
- the thickness of the release sheet is not particularly limited, but is preferably 10-200 ⁇ m, more preferably 20-150 ⁇ m.
- the method for producing the adhesive tape of the present invention is not particularly limited, and it can be produced by a known method.
- a method for producing an adhesive tape having a substrate, an adhesive layer provided on one side of the substrate, and a buffer layer provided on the other side of the substrate is as follows. be.
- the buffer layer is formed from a buffer layer-forming composition containing an energy ray-polymerizable compound, a buffer layer provided by coating and curing the buffer layer-forming composition on a release sheet, and a substrate; and removing the release sheet, a laminate of the buffer layer and the substrate is obtained.
- the buffer layer is a layer containing a polyolefin resin film, a laminate of the buffer layer and the base material can be obtained by bonding the buffer layer and the base material together.
- the adhesive layer provided on the release sheet can be attached to the substrate side of the laminate to manufacture an adhesive tape in which the release sheet is attached to the surface of the adhesive layer.
- the release sheet attached to the surface of the pressure-sensitive adhesive layer may be peeled off and removed before use of the pressure-sensitive adhesive tape.
- an adhesive (adhesive composition) is directly applied on a release sheet by a known coating method, and the coating film is dried by heating to form an adhesive layer. Layers can be formed.
- an adhesive may be directly applied to one side of the substrate to form an adhesive layer.
- the method of applying the pressure-sensitive adhesive include the spray coating method, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, etc. shown in the manufacturing method of the buffer layer.
- the composition for forming the buffer layer is directly applied on the release sheet by a known coating method to form a coating film, and the coating film is irradiated with energy rays.
- a buffer layer can be formed.
- the buffer layer may be formed by directly applying the composition for forming a buffer layer on one side of the base material and drying it by heating or by irradiating the coating film with energy rays.
- Examples of methods for applying the buffer layer-forming composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
- an organic solvent may be added to the composition for forming a buffer layer, and the composition may be applied in the form of a solution onto the release sheet.
- the composition for forming a buffer layer contains an energy ray-polymerizable compound
- the hardening of the buffer layer may be performed in one hardening process, or may be performed in multiple times.
- the coating film on the release sheet may be completely cured to form a buffer layer and then attached to the base material, and a semi-cured buffer layer forming film may be formed without completely curing the coating film. Then, after bonding the buffer layer-forming film to the base material, the energy beam may be irradiated again to completely cure the film, thereby forming the buffer layer.
- Ultraviolet rays are preferable as the energy rays to be irradiated in the curing treatment.
- the coating film of the composition for forming a buffer layer may be exposed, but the coating film is covered with a release sheet or base material, and the energy beam is irradiated in a state where the coating film is not exposed. Curing is preferred.
- the cushioning layer is a layer containing a polyolefin resin film
- the cushioning layer and the substrate may be bonded together by extrusion lamination.
- the polyolefin resin constituting the buffer layer is melted and kneaded, and while moving the base material at a constant speed, on one side of the base material, Extrusion lamination of molten polyolefin resin.
- the buffer layer may be directly laminated on the substrate by heat sealing or the like.
- it may be laminated via an easy-adhesion layer by a method such as a dry lamination method.
- the method for producing an adhesive tape having buffer layers on both sides of a base material is, for example, by obtaining a laminate in which a buffer layer, a base material, and a buffer layer are laminated in this order by the method described above, and then A pressure-sensitive adhesive layer may be formed on the buffer layer side.
- the adhesive tape according to the present invention is preferably used when the back surface of the wafer is ground after being attached to the front surface of a semiconductor wafer. More preferably, the pressure-sensitive adhesive tape according to the present invention is preferably used in DBG in which wafer backside grinding and wafer singulation are performed simultaneously. Particularly preferably, the adhesive tape according to the present invention is preferably used for LDBG in which a group of chips with a small kerf width can be obtained when a semiconductor wafer is singulated.
- chip group refers to a plurality of semiconductor chips arranged in a wafer shape and held on the adhesive tape according to the present invention.
- the method for manufacturing a semiconductor device includes at least steps 1 to 4 below.
- Step 1 A step of applying the above adhesive tape to the surface of a semiconductor wafer and cutting the adhesive tape along the outer periphery of the semiconductor wafer
- Step 2 Forming a groove from the front surface side of the semiconductor wafer, or forming a groove on the front surface or the back surface of the semiconductor wafer
- Step 3 The semiconductor wafer with the adhesive tape attached to the surface and the groove or modified region formed is ground from the back side to form the groove or modified region
- Step 4 A step of peeling the adhesive tape from the singulated semiconductor wafer (that is, a plurality of semiconductor chips)
- Step 1 the adhesive tape of the present invention is attached to the surface of a semiconductor wafer via an adhesive layer, and cut along the outer circumference of the semiconductor wafer.
- the adhesive tape is attached so as to cover the semiconductor wafer and the peripheral table extending around its periphery.
- the adhesive tape is cut by a cutter or the like along the outer periphery of the semiconductor wafer.
- the cutting speed is usually 10-300 mm/s.
- the temperature of the cutter blade during cutting may be room temperature, or the cutting may be performed by heating the cutter blade.
- step 1 may be performed before step 2, which will be described later, or after step 2.
- step 1 is preferably performed before step 2.
- step 1 is performed after step 2.
- the semiconductor wafer used in this manufacturing method may be a silicon wafer, a wafer of gallium arsenide, silicon carbide, lithium tantalate, lithium niobate, gallium nitride, indium phosphide, or the like, or a glass wafer. .
- the thickness of the semiconductor wafer before grinding is not particularly limited, it is usually about 500 to 1000 ⁇ m.
- a semiconductor wafer usually has a circuit formed on its surface. Formation of circuits on the wafer surface can be performed by various methods including conventional methods such as an etching method and a lift-off method.
- Step 2 grooves are formed from the front surface side of the semiconductor wafer, or modified regions are formed inside the semiconductor wafer from the front surface or rear surface of the semiconductor wafer.
- the grooves formed in this process are shallower than the thickness of the semiconductor wafer.
- the grooves can be formed by dicing using a conventionally known wafer dicing device or the like. Also, the semiconductor wafer is divided into a plurality of semiconductor chips along the grooves in step 3, which will be described later.
- the modified region is an embrittled portion of the semiconductor wafer, and the semiconductor wafer is thinned by grinding in the grinding process, or the semiconductor wafer is destroyed by grinding force, resulting in a semiconductor chip.
- This is the region that becomes the starting point for individualization into . That is, in step 2, the grooves and modified regions are formed along dividing lines along which the semiconductor wafer is divided into individual semiconductor chips in step 3, which will be described later.
- the modified region is formed by irradiating laser focused on the inside of the semiconductor wafer, and the modified region is formed inside the semiconductor wafer.
- the laser irradiation may be performed from the front side or the back side of the semiconductor wafer.
- the laser is applied to the semiconductor wafer through the adhesive tape.
- the semiconductor wafer on which the adhesive tape is attached and the grooves or modified regions are formed is placed on the chuck table and is held by suction on the chuck table. At this time, the semiconductor wafer is sucked with its surface side arranged on the table side.
- Step 3 After steps 1 and 2, the back surface of the semiconductor wafer on the chuck table is ground to singulate the semiconductor wafer into a plurality of semiconductor chips.
- the back surface grinding is performed so as to thin the semiconductor wafer at least to the position reaching the bottom of the groove. By this back-grinding, the grooves become cuts penetrating the wafer, and the semiconductor wafer is divided by the cuts into individual semiconductor chips.
- the ground surface may reach the modified region by grinding, but it does not have to reach the modified region strictly. That is, the semiconductor wafer may be ground from the modified region to a position close to the modified region so that the semiconductor wafer is broken into individual semiconductor chips starting from the modified region.
- the actual singulation of the semiconductor chips may be performed by applying a pick-up tape, which will be described later, and then stretching the pick-up tape.
- dry polishing may be performed prior to picking up the chips.
- the shape of the individualized semiconductor chips may be a square or an elongated shape such as a rectangle.
- the thickness of the individualized semiconductor chips is not particularly limited, it is preferably about 5 to 100 ⁇ m, more preferably 10 to 45 ⁇ m.
- LDBG a modified region is provided inside the wafer with a laser, and the wafer is singulated by stress or the like during wafer backside grinding. ⁇ 45 ⁇ m becomes easy.
- the size of the individualized semiconductor chips is not particularly limited, but the chip size is preferably less than 600 mm 2 , more preferably less than 400 mm 2 , and even more preferably less than 300 mm 2 .
- Step 4 The adhesive tape is peeled off from the semiconductor wafer (that is, a plurality of semiconductor chips aligned in a wafer shape) that has been separated into pieces.
- This step is performed, for example, by the following method. First, when the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is formed from an energy ray-curable pressure-sensitive adhesive, the pressure-sensitive adhesive layer is cured by irradiation with energy rays. Next, a pick-up tape is attached to the rear surface side of the separated semiconductor wafer, and the position and direction are aligned so that pick-up is possible.
- the ring frame arranged on the outer peripheral side of the wafer is also adhered to the pick-up tape, and the outer peripheral edge of the pick-up tape is fixed to the ring frame.
- the wafer and the ring frame may be attached to the pickup tape at the same time, or may be attached at separate timings.
- the adhesive tape is peeled off from the plurality of semiconductor chips held on the pickup tape.
- the pickup tape is not particularly limited, it is composed of, for example, a base material and an adhesive tape provided with an adhesive layer provided on at least one surface of the base material.
- an adhesive tape can be used instead of the pickup tape.
- the adhesive tape includes a laminate of a film-like adhesive and a release sheet, a laminate of a dicing tape and a film-like adhesive, and an adhesive layer and a release sheet that function as both a dicing tape and a die bonding tape.
- a dicing die bonding tape and the like can be mentioned. That is, the present embodiment may include a step of attaching a dicing die bonding tape to the back surface of the semiconductor wafer.
- a film-like adhesive may be applied to the back side of the semiconductor wafer that has been divided into individual pieces. When a film adhesive is used, the film adhesive may have the same shape as the wafer.
- the adhesive layer of the adhesive tape is formed from an energy ray-curable adhesive
- the portion of the adhesive layer that is in close contact with the wafer is cured, and the adhesive strength of that portion is increased. drops sufficiently.
- the curing of the adhesive is usually inhibited by the oxygen in the atmosphere. power is not reduced enough.
- the thickness of the semiconductor wafer is extremely thinned to about 30 ⁇ m by back grinding, if a dicing die bonding tape or the like is attached to the back surface of the semiconductor wafer, the surface of the semiconductor wafer will not be smooth.
- the uncured portion of the adhesive layer of the attached adhesive tape contacts and sticks to the adhesive layer of the dicing die bonding tape or the like.
- the adhesive tape attached to the dicing/die-bonding tape or the like is peeled off, the adhesive tape and the dicing/die-bonding tape are integrated, and the dicing/die-bonding tape is also curved as the adhesive tape is curved.
- the wafer or chip sandwiched between the adhesive tape and the dicing/die-bonding tape also bends. As a result, cracks are likely to occur in the chip.
- the adhesive layer of the dicing die bonding tape or the like may be damaged by bending, and the fragments may fall off.
- FIG. 5 is a schematic diagram of a laminate obtained by attaching a dicing die bonding tape 30 to the semiconductor wafer 20 after back grinding to which the adhesive tape according to the present embodiment is attached.
- FIG. 5 shows a case where a dicing die bonding tape 30 is attached to a semiconductor wafer 20 whose back surface has been ground to an extremely thin thickness of about 30 ⁇ m.
- the pressure-sensitive adhesive tape according to the present embodiment even when the pressure-sensitive adhesive layer is exposed to the atmosphere, the pressure-sensitive adhesive strength can be sufficiently reduced by irradiation with energy rays. Therefore, as shown in FIG.
- the plurality of semiconductor chips on the adhesive tape or the pick-up tape is a semiconductor. It is picked up together with the adhesive layer divided into the same shape as the chip. Then, the semiconductor chip is fixed on a substrate or the like via an adhesive layer to manufacture a semiconductor device. The division of the adhesive layer is performed by laser or expansion.
- the adhesive tape according to the present invention is used in a method for singulating semiconductor wafers by DBG or LDBG. It can be preferably used for LDBG where a group of chips having a smaller width and thinner can be obtained.
- the adhesive tape according to the present invention can also be used for normal back grinding, and can also be used to temporarily hold a workpiece during processing of glass, ceramics, etc. It can also be used. It can also be used as various removable adhesive tapes.
- the adhesive tape was applied to a silicon wafer having a diameter of 12 inches and a thickness of 775 ⁇ m using a tape laminator for back grinding (manufactured by Lintec, device name: RAD-3510F/12), and cut along the periphery of the silicon wafer.
- a laser saw manufactured by Disco, device name "DFL7361"
- a silicon wafer is irradiated with a laser beam having a wavelength of 1342 nm from the surface of the silicon wafer, and the chip size becomes 5 mm ⁇ 5 mm inside the silicon wafer.
- the modified region was formed.
- the adhesive tape was sized to cover the outer periphery of the silicon wafer after grinding, and was 1.0 mm larger than the outer periphery of the silicon wafer.
- an ultraviolet irradiation device manufactured by Lintec, device name “RAD 2000”
- the adhesive tape is irradiated with ultraviolet rays under the conditions of an illuminance of 220 mW/cm 2 and a light intensity of 500 mJ/cm 2 from the substrate side, that is, from the surface side of the silicon wafer. did.
- the adhesive layer surface of the dicing die bonding tape (Lintec Co., Ltd., LD01D-07) is heated to 60 ° C. using a tape mounter (Lintec Co., device name "ADWILL RAD-2700") to the back surface of the silicon wafer. affixed.
- the adhesive tape was peeled off. At this time, the degree of peeling of the adhesive layer of the dicing die bonding tape was observed and evaluated according to the following criteria.
- B The peeled area is 70% or more and less than 97%.
- C The peeled area is 97% or more.
- a silicon nitride cantilever (“SCANASYST-AIR” manufactured by Bruker Corporation) installed in an atomic force microscope (manufactured by Bruker Corporation, device name “Dimension Icon”), nominal tip radius: 2 nm, resonance frequency: 70 kHz, spring constant : 0.4 N/m) at room temperature, the surface of the pressure-sensitive adhesive layer was pressed with a pressing amount of 5 nm and a scanning speed of 5 Hz, and separated.
- the surface elastic modulus was calculated by fitting the obtained force curve curve (horizontal axis is sample deformation amount, vertical axis is measurement load) with JKR theoretical formula.
- the average value of the values obtained by measuring 4096 points on the surface of the pressure-sensitive adhesive layer (5 ⁇ m ⁇ 5 ⁇ m) was defined as the surface elastic modulus (MPa).
- Adhesion energy Regarding the adhesive tape for semiconductor processing, one surface of the adhesive layer is exposed to the atmosphere, and an ultraviolet irradiation device ( manufactured by Lintec, device name “RAD 2000”) is used to illuminate at 220 mW / cm and light intensity is 500 mJ / cm. Under the conditions of 2 , the adhesive tape was irradiated with ultraviolet rays from the substrate side.
- an ultraviolet irradiation device manufactured by Lintec, device name “RAD 2000”
- a silicon nitride cantilever (“SCANASYST-AIR” manufactured by Bruker Corporation) installed in an atomic force microscope (manufactured by Bruker Corporation, device name “Dimension Icon”), nominal tip radius: 2 nm, resonance frequency: 70 kHz, spring constant : 0.4 N/m) at room temperature, the surface of the pressure-sensitive adhesive layer was pressed with a pressing amount of 5 nm and a scanning speed of 5 Hz, and separated. The surface elastic modulus was calculated by fitting the obtained force curve curve (horizontal axis is sample deformation amount, vertical axis is measurement load) with JKR theoretical formula. The average value of the values obtained by measuring 4096 points on the surface of the pressure-sensitive adhesive layer (5 ⁇ m ⁇ 5 ⁇ m) was taken as the adhesion energy (J/m 2 ).
- ⁇ Example 1> Substrate As a substrate, a PET film with an easily adhesive layer on both sides (Cosmoshine A4300 manufactured by Toyobo Co., Ltd., thickness: 50 ⁇ m, Young's modulus at 23° C.: 2550 MPa) was prepared.
- Adhesive layer preparation of adhesive composition
- An acrylic polymer obtained by copolymerizing 50 parts by mass of n-butyl acrylate (BA), 20 parts by mass of methyl methacrylate (MMA), and 30 parts by mass of 2-hydroxyethyl methacrylate (HEMA), 2-Methacryloyloxyethyl isocyanate (MOI) was reacted so as to be added to 90 mol % of hydroxyl groups out of all the hydroxyl groups in the above to obtain an energy ray-curable acrylic resin.
- Example 2 In the preparation of the adhesive composition, 50 parts by weight of n-butyl acrylate (BA), 20 parts by weight of methyl methacrylate (MMA), 15 parts by weight of 2-hydroxyethyl acrylate (HEA), and 15 parts by weight of 2-hydroxyethyl methacrylate (HEMA) A pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that the acrylic polymer was obtained by copolymerizing parts by mass.
- BA n-butyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- Example 3 In preparing the adhesive composition, 60 parts by mass of ethyl acrylate (EA), 10 parts by mass of methyl methacrylate (MMA), and 30 parts by mass of 2-hydroxyethyl methacrylate (HEMA) are copolymerized to obtain an acrylic polymer. , 2,2-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins B.V., product A pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that 2.4 parts by mass of OMNIRAD 651) was used.
- EA ethyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- Example 4 In the preparation of the pressure-sensitive adhesive composition, 60 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl methacrylate (MMA), and 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) are copolymerized to form an acrylic polymer. and 2,2-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins B.V.) instead of 3.3 parts by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator. , product name "OMNIRAD 651”) was used in the same manner as in Example 1, except that 2.4 parts by mass was used to prepare an adhesive tape for semiconductor processing.
- BA n-butyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- Example 5 In the preparation of the adhesive composition, 65 parts by weight of n-butyl acrylate (BA), 5 parts by weight of methyl methacrylate (MMA), and 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) are copolymerized to form an acrylic polymer. and 2,2-dimethoxy-2-phenylacetophenone (manufactured by IGM Resins B.V.) instead of 3.3 parts by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator. , product name "OMNIRAD 651”) was used in the same manner as in Example 1, except that 2.4 parts by mass was used to prepare an adhesive tape for semiconductor processing.
- BA n-butyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- Example 6> In the preparation of the adhesive composition, 60 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of methyl methacrylate (MMA), and 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) are copolymerized to form an acrylic polymer. 2,2-dimethoxy-2-phenylacetophenone (IGM Resins B.V. A pressure-sensitive adhesive tape for semiconductor processing was prepared in the same manner as in Example 1, except that 2.4 parts by mass of OMNIRAD 651 (manufactured by Co., Ltd.) was used.
- OMNIRAD 651 manufactured by Co., Ltd.
- Example 7 In the preparation of the adhesive composition, 40 parts by weight of 2-ethylhexyl acrylate (2EHA), 20 parts by weight of ethyl acrylate (EA), 10 parts by weight of methyl methacrylate (MMA), and 30 parts by weight of 2-hydroxyethyl methacrylate (HEMA) to obtain an acrylic polymer, and replace 3.3 parts by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator with 2,2-dimethoxy-2-
- EHA 2-ethylhexyl acrylate
- EA ethyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- a pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that 2.4 parts by mass of phenylacetophenone (manufactured by IGM Resins B.V., product name "OMNIRAD 651”) was used.
- Example 8> In the preparation of the adhesive composition, 60 parts by weight of ethyl acrylate (EA), 10 parts by weight of methyl methacrylate (MMA), 15 parts by weight of 2-hydroxyethyl acrylate (HEA), and 15 parts by weight of 2-hydroxyethyl methacrylate (HEMA) to obtain an acrylic polymer, and 2,2-dimethoxy-2-phenyl instead of 3.3 parts by mass of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator.
- a pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that 2.4 parts by mass of acetophenone (manufactured by IGM Resins B.V., product name "OMNIRAD 651”) was used.
- Example 9 In the preparation of the adhesive composition, 60 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl methacrylate (MMA), 15 parts by weight of 2-hydroxyethyl acrylate (HEA), and 15 parts by weight of 2-hydroxyethyl methacrylate (HEMA) 2,2-dimethoxy-2 in place of 3.3 parts by weight of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide as a photopolymerization initiator to obtain an acrylic polymer by copolymerizing parts by weight of
- a pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that 2.4 parts by mass of -phenylacetophenone (manufactured by IGM Resins B.V., product name "OMNIRAD 651”) was used.
- Example 10 In the preparation of the adhesive composition, 52 parts by weight of n-butyl acrylate (BA), 20 parts by weight of methyl methacrylate (MMA), 21 parts by weight of 2-hydroxyethyl acrylate (HEA), and 2-hydroxyethyl methacrylate (HEMA) A pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that 7 parts by mass of the polymer was copolymerized to obtain an acrylic polymer.
- BA n-butyl acrylate
- MMA methyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- HEMA 2-hydroxyethyl methacrylate
- ⁇ Comparative Example 1> In the preparation of the pressure-sensitive adhesive composition, 52 parts by mass of n-butyl acrylate (BA), 20 parts by mass of methyl methacrylate (MMA), and 28 parts by mass of 2-hydroxyethyl acrylate (HEA) are copolymerized to form an acrylic polymer. A pressure-sensitive adhesive tape for semiconductor processing was produced in the same manner as in Example 1, except that it was obtained.
- BA n-butyl acrylate
- MMA methyl methacrylate
- HOA 2-hydroxyethyl acrylate
- the peel strength of the adhesive tape for semiconductor processing according to the present invention is sufficiently reduced even in the atmosphere by irradiation with energy rays such as ultraviolet rays. Therefore, by using the adhesive tape according to the present invention, even when the thickness of the semiconductor wafer is extremely thinned by back-grinding, the occurrence of cracks in the semiconductor chip can be suppressed, and the productivity of the semiconductor device can be improved.
- Adhesive tape 10 adhesive tape 20 semiconductor wafer 30 adhesive tape (dicing die bonding tape) REFERENCE SIGNS LIST 100 Adhesive tape according to the present embodiment 110 Base material 120 Adhesive layer
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Abstract
Description
前記粘着剤層の一面を大気雰囲気に露出した状態で、照度220mW/cm2および光量500mJ/cm2の条件で前記粘着テープに紫外線を照射し、当該粘着剤層の露出した面に、23℃、50%RHにおいてPMMA板を2kgロールで1往復の条件で貼り付けて30分間放置した後、当該粘着テープを180°剥離するときの剥離強度が、1600mN/25mm以下である、半導体加工用粘着テープ。
前記アクリル系樹脂全量100質量部に対し、HEMA由来の重合単位の含有量が6質量部以上である、(1)に記載の半導体加工用粘着テープ。
前記半導体ウエハの表面側から溝を形成し、又は前記半導体ウエハの表面若しくは裏面から半導体ウエハ内部に改質領域を形成する工程と、
前記粘着テープが表面に貼付され、かつ前記溝又は前記改質領域が形成された半導体ウエハを、裏面側から研削して、前記溝又は前記改質領域を起点として複数のチップに個片化させる工程と、
前記複数のチップから前記粘着テープを剥離する工程と、
を備える半導体装置の製造方法。
本明細書において、例えば「(メタ)アクリレート」とは、「アクリレート」及び「メタクリレート」の双方を示す語として用いており、他の類似用語についても同様である。
半導体ウエハの「表面」とは回路が形成された面を指し、「裏面」とは回路が形成されていない面を指す。
半導体ウエハの個片化とは、半導体ウエハを回路毎に分割し、半導体チップを得ることを言う。
以下に、本実施形態に係る半導体加工用粘着テープの各部材の構成をさらに詳細に説明する。
本実施形態に係る粘着テープにおいて、粘着剤層の一面を大気雰囲気に露出した状態で、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を照射し、当該粘着剤層の露出した面に、23℃、50%RHにおいてPMMA板を2kgロールで1往復の条件で貼り付けて30分間放置した後、当該粘着テープを180°剥離するときの剥離強度は、1600mN/25mm以下であり、好ましくは1100mN/25mm以下であり、より好ましくは980mN/25mm以下であり、さらに好ましくは800mN/25mm以下である。上記剥離強度を上記範囲とすることで、粘着剤層の粘着力を十分に低下でき、その結果、チップのクラックの発生を抑制できる。また、上記剥離強度の下限は、特に制限されないが、通常50N/25mmであり、好ましくは80N/25mmである。
粘着剤層を形成するエネルギー線硬化性粘着剤としては、例えば、非エネルギー線硬化性の粘着性樹脂(「粘着性樹脂I」ともいう)に加え、粘着性樹脂以外のエネルギー線硬化性化合物を含むエネルギー線硬化性粘着剤組成物(以下、「X型の粘着剤組成物」ともいう)が使用可能である。また、エネルギー線硬化性粘着剤として、非エネルギー線硬化性の粘着性樹脂の側鎖に不飽和基を導入したエネルギー線硬化性の粘着性樹脂(以下、「粘着性樹脂II」ともいう)を主成分として含み、粘着性樹脂以外のエネルギー線硬化性化合物を含まない粘着剤組成物(以下、「Y型の粘着剤組成物」ともいう)も使用してもよい。
これらの中では、XY型の粘着剤組成物を使用することが好ましい。XY型のものを使用することで、硬化前においては十分な粘着特性を有する一方で、硬化後においては、半導体ウエハに対する剥離強度を十分に低くすることが可能である。
以下、粘着性樹脂として、アクリル系樹脂が使用されるアクリル系粘着剤についてより詳述に説明する。
また、アクリル系重合体は、上記以外にも、スチレン、α-メチルスチレン、ビニルトルエン、蟻酸ビニル、酢酸ビニル、アクリロニトリル、アクリルアミド等の上記のアクリル系モノマーと共重合可能なモノマー由来の構成単位を含んでもよい。
また、不飽和基含有化合物が有する、官能基と結合可能な置換基としては、イソシアネート基やグリシジル基等が挙げられる。したがって、不飽和基含有化合物としては、例えば、(メタ)アクリロイルオキシエチルイソシアネート、(メタ)アクリロイルイソシアネート、グリシジル(メタ)アクリレート等が挙げられる。
なお、アクリル系樹脂の重量平均分子量(Mw)は、好ましくは30万~160万、より好ましくは40万~140万、さらに好ましくは50万~120万である。
X型又はXY型の粘着剤組成物に含有されるエネルギー線硬化性化合物としては、分子内に不飽和基を有し、エネルギー線照射により重合硬化可能なモノマー又はオリゴマーが好ましい。
このようなエネルギー線硬化性化合物としては、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトール(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、1,4-ブチレングリコールジ(メタ)アクリレート、1,6-へキサンジオール(メタ)アクリレート等の多価(メタ)アクリレートモノマー、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート,ポリエーテル(メタ)アクリレート、エポキシ(メタ)アクリレート等のオリゴマーが挙げられる。
エネルギー線硬化性化合物の分子量(オリゴマーの場合は重量平均分子量)は、好ましくは100~12000、より好ましくは200~10000、さらに好ましくは400~8000、特に好ましくは600~6000である。
一方で、XY型の粘着剤組成物におけるエネルギー線硬化性化合物の含有量は、粘着性樹脂100質量部に対して、好ましくは1~30質量部、より好ましくは2~20質量部、さらに好ましくは3~15質量部である。XY型の粘着剤組成物では、粘着性樹脂が、エネルギー線硬化性であるため、エネルギー線硬化性化合物の含有量が少なくても、エネルギー線照射後、十分に剥離強度を低下させることが可能である。
粘着剤組成物は、さらに架橋剤を含有することが好ましい。架橋剤は、例えば粘着性樹脂が有する官能基含有モノマー由来の官能基に反応して、粘着性樹脂同士を架橋するものである。架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等、及びそれらのアダクト体等のイソシアネート系架橋剤;エチレングリコールグリシジルエーテル等のエポキシ系架橋剤;ヘキサ〔1-(2-メチル)-アジリジニル〕トリフオスファトリアジン等のアジリジン系架橋剤;アルミニウムキレート等のキレート系架橋剤;等が挙げられる。これらの架橋剤は、単独で又は2種以上を組み合わせて用いてもよい。
架橋剤の配合量は、架橋反応を促進させる観点から、粘着性樹脂100質量部に対して、好ましくは0.01~10質量部、より好ましくは0.03~7質量部、さらに好ましくは0.05~4質量部である。
また、粘着剤組成物がエネルギー線硬化性である場合には、粘着剤組成物は、さらに光重合開始剤を含有することが好ましい。光重合開始剤を含有することで、紫外線等の比較的低エネルギーのエネルギー線でも、粘着剤組成物の硬化反応を十分に進行させることができる。
光重合開始剤の配合量は、粘着性樹脂100質量部に対して、好ましくは0.01~10質量部、より好ましくは0.03~5質量部、さらに好ましくは0.05~5質量部である。
粘着性組成物は、本発明の効果を損なわない範囲において、その他の添加剤を含有してもよい。その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤(可塑剤)、充填剤、防錆剤、顔料、染料等が挙げられる。これらの添加剤を配合する場合、添加剤の配合量は、粘着性樹脂100質量部に対して、好ましくは0.01~6質量部である。
有機溶媒としては、例えば、メチルエチルケトン、アセトン、酢酸エチル、テトラヒドロフラン、ジオキサン、シクロヘキサン、n-ヘキサン、トルエン、キシレン、n-プロパノール、イソプロパノール等が挙げられる。
なお、これらの有機溶媒は、粘着性樹脂の合成時に使用された有機溶媒をそのまま用いてもよいし、該粘着剤組成物の溶液を均一に塗布できるように、合成時に使用された有機溶媒以外の1種以上の有機溶媒を加えてもよい。
基材は、23℃におけるヤング率が1000MPa以上であることが好ましい。ヤング率が1000MPa未満の基材を使用すると、粘着テープによる半導体ウエハ又は半導体チップに対する保持性能が低下し、裏面研削時の振動等を抑制することができず、半導体チップの欠けや破損が発生しやすくなる。一方、基材の23℃におけるヤング率を1000MPa以上とすることで、粘着テープによる半導体ウエハ又は半導体チップに対する保持性能が高まり、裏面研削時の振動等を抑制し、半導体チップの欠けや破損を防止できる。また、粘着テープを半導体チップから剥離する際の応力を小さくすることが可能になり、テープ剥離時に生じるチップ欠けや破損を防止できる。さらに、粘着テープを半導体ウエハに貼付する際の作業性も良好にすることが可能である。このような観点から、基材の23℃におけるヤング率は、より好ましくは1800~30000MPa、さらに好ましくは2500~6000MPaである。
これら樹脂フィルムの中でも、ポリエステルフィルム、ポリアミドフィルム、ポリイミドフィルム、二軸延伸ポリプロピレンフィルムから選ばれる1種以上を含むフィルムが好ましく、ポリエステルフィルムを含むことがより好ましく、ポリエチレンテレフタレートフィルムを含むことがさらに好ましい。
また、基材の少なくとも一方の表面には、緩衝層及び粘着剤層の少なくとも一方との密着性を向上させるために、コロナ処理等の接着処理を施してもよい。また、基材は、上記した樹脂フィルムと、樹脂フィルムの少なくとも一方の表面に被膜された易接着層とを有しているものでもよい。
易接着層の厚さとしては、好ましくは0.01~10μm、より好ましくは0.03~5μmである。なお、本願実施例における易接着層の厚さは、基材の厚さに対して小さいため、易接着層を有する樹脂フィルムの厚みと基材の厚みとは実質的に同一である。また、易接着層の材質は柔らかいため、ヤング率に与える影響は小さく、基材のヤング率は、易接着層を有する場合でも、樹脂フィルムのヤング率と実質的に同一である。
本実施形態に係る粘着テープは、緩衝層を有していてもよい。緩衝層は、基材の少なくとも一方の面に設けることができ、基材の両面に設けることもできる。また、基材の一方の面に粘着剤層を設け、基材の他方の面に緩衝層を設けることもできる。
以下、エネルギー線重合性化合物を含む緩衝層形成用組成物から形成される層に含まれる各成分、ポリオレフィン樹脂フィルムを含む層に含まれる各成分について順に説明する。
エネルギー線重合性化合物を含む緩衝層形成用組成物は、エネルギー線が照射されることで硬化することが可能になる。
また、エネルギー線重合性化合物を含む緩衝層形成用組成物は、より具体的には、ウレタン(メタ)アクリレート(a1)を含むことが好ましい。また、緩衝層形成用組成物は、上記(a1)に加えて、環形成原子数6~20の脂環基又は複素環基を有する重合性化合物(a2)及び/又は官能基を有する重合性化合物(a3)を含有することがより好ましい。また、緩衝層形成用組成物は、上記(a1)~(a3)成分に加えて、多官能重合性化合物(a4)を含有してもよい。さらに、緩衝層形成用組成物は光重合開始剤を含有することが好ましく、本発明の効果を損なわない範囲において、その他の添加剤や樹脂成分を含有してもよい。
以下、エネルギー線重合性化合物を含む緩衝層形成用組成物中に含まれる各成分について詳細に説明する。
ウレタン(メタ)アクリレート(a1)とは、少なくとも(メタ)アクリロイル基及びウレタン結合を有する化合物であり、エネルギー線照射により重合硬化する性質を有するものである。ウレタン(メタ)アクリレート(a1)は、オリゴマーまたはポリマーである。
成分(a1)は、例えば、ポリオール化合物と、多価イソシアネート化合物とを反応させて得られる末端イソシアネートウレタンプレポリマーに、ヒドロキシル基を有する(メタ)アクリレートを反応させて得ることができる。なお、成分(a1)は、単独で又は2種以上を組み合わせて用いてもよい。
なお、ポリオール化合物としては、2官能のジオール、3官能のトリオール、4官能以上のポリオールのいずれであってもよいが、2官能のジオールが好ましく、ポリエステル型ジオールまたはポリカーボネート型ジオールがより好ましい。
これらの中でも、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネートが好ましい。
これらの中でも、ヒドロキシアルキル(メタ)アクリレートが好ましく、2-ヒドロキシエチル(メタ)アクリレートがより好ましい。
緩衝層形成用組成物中の成分(a1)の含有量は、緩衝層形成用組成物の全量(100質量部)に対して、好ましくは10~70質量部、より好ましくは20~60質量部である。
成分(a2)は、環形成原子数6~20の脂環基又は複素環基を有する重合性化合物であり、さらには、少なくとも1つの(メタ)アクリロイル基を有する化合物であることが好ましく、より好ましくは1つの(メタ)アクリロイル基を有する化合物である。成分(a2)を用いることで、得られる緩衝層形成用組成物の成膜性を向上させることができる。
なお、環形成原子数とは、原子が環状に結合した構造の化合物の当該環自体を構成する原子の数を表し、環を構成しない原子(例えば、環を構成する原子に結合した水素原子)や、当該環が置換基によって置換される場合の置換基に含まれる原子は環形成原子数には含まない。
なお、成分(a2)は、単独で又は2種以上を組み合わせて用いてもよい。
脂環基含有(メタ)アクリレートの中ではイソボルニル(メタ)アクリレートが好ましく、複素環基含有(メタ)アクリレートの中ではテトラヒドロフルフリル(メタ)アクリレートが好ましい。
成分(a3)は、水酸基、エポキシ基、アミド基、アミノ基等の官能基を含有する重合性化合物であり、さらには、少なくとも1つの(メタ)アクリロイル基を有する化合物であることが好ましく、より好ましくは1つの(メタ)アクリロイル基を有する化合物である。
成分(a3)は、成分(a1)との相溶性が良好であり、緩衝層形成用組成物の粘度を適度な範囲に調整しやすくなる。また、緩衝層を比較的薄くしても緩衝性能が良好になる。
成分(a3)としては、例えば、水酸基含有(メタ)アクリレート、エポキシ基含有化合物、アミド基含有化合物、アミノ基含有(メタ)アクリレート等が挙げられる。
エポキシ基含有化合物としては、例えば、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート、アリルグリシジルエーテル等が挙げられ、これらの中では、グリシジル(メタ)アクリレート、メチルグリシジル(メタ)アクリレート等のエポキシ基含有(メタ)アクリレートが好ましい。
アミド基含有化合物としては、例えば、(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等が挙げられる。
アミノ基含有(メタ)アクリレートとしては、例えば、第1級アミノ基含有(メタ)アクリレート、第2級アミノ基含有(メタ)アクリレート、第3級アミノ基含有(メタ)アクリレート等が挙げられる。
なお、成分(a3)は、単独で又は2種以上を組み合わせて用いてもよい。
また、緩衝層形成用組成物中の成分(a2)と成分(a3)との含有量比〔(a2)/(a3)〕は、好ましくは0.5~3.0、より好ましくは1.0~3.0、さらに好ましくは1.3~3.0、特に好ましくは1.5~2.8である。
多官能重合性化合物とは、光重合性不飽和基を2つ以上有する化合物をいう。光重合性不飽和基は、炭素-炭素二重結合を含む官能基であり、例えば、(メタ)アクリロイル基、ビニル基、アリル基、ビニルベンジル基等が挙げられる。光重合性不飽和基は2種以上を組み合わせてもよい。多官能重合性化合物中の光重合性不飽和基と成分(a1)中の(メタ)アクリロイル基とが反応したり、成分(a4)中の光重合性不飽和基同士が反応することで、三次元網目構造(架橋構造)が形成される。多官能重合性化合物を使用すると、光重合性不飽和基を1つしか含まない化合物を使用した場合と比較して、エネルギー線照射により形成される架橋構造が増加しやすい。
ルアミド等が挙げられる。
なお、成分(a4)は、単独で又は2種以上を組み合わせて用いてもよい。
これらの中でも、ジペンタエリスリトールヘキサ(メタ)アクリレートが好ましい。
緩衝層形成用組成物には、本発明の効果を損なわない範囲において、上記の成分(a1)~(a4)以外のその他の重合性化合物(a5)を含有してもよい。
成分(a5)としては、例えば、炭素数1~20のアルキル基を有するアルキル(メタ)アクリレート;スチレン、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、N-ビニルホルムアミド、N-ビニルピロリドン、N-ビニルカプロラクタム等のビニル化合物:等が挙げられる。なお、成分(a5)は、単独で又は2種以上を組み合わせて用いてもよい。
緩衝層形成用組成物には、緩衝層を形成する際、光照射による重合時間を短縮させ、また、光照射量を低減させる観点から、さらに光重合開始剤を含有することが好ましい。
緩衝層形成用組成物には、本発明の効果を損なわない範囲において、その他の添加剤を含有してもよい。その他の添加剤としては、例えば、帯電防止剤、酸化防止剤、軟化剤(可塑剤)、充填剤、防錆剤、顔料、染料等が挙げられる。これらの添加剤を配合する場合、緩衝層形成用組成物中の各添加剤の含有量は、エネルギー線重合性化合物の合計量100質量部に対して、好ましくは0.01~6質量部、より好ましくは0.1~3質量部である。
緩衝層形成用組成物には、本発明の効果を損なわない範囲において、樹脂成分を含有してもよい。樹脂成分としては、例えば、ポリエン・チオール系樹脂や、ポリブテン、ポリブタジエン、ポリメチルペンテン等のポリオレフィン系樹脂、及びスチレン系共重合体等の熱可塑性樹脂等が挙げられる。
緩衝層形成用組成物中のこれらの樹脂成分の含有量は、緩衝層形成用組成物の全量(100質量部)に対して、好ましくは0~20質量部、より好ましくは0~10質量部、さらに好ましくは0~5質量部、特に好ましくは0~2質量部である。
したがって、当該緩衝層は、成分(a1)由来の重合単位を含む。また、当該緩衝層は、成分(a2)由来の重合単位及び/又は成分(a3)由来の重合単位を含有することが好ましい。さらに、成分(a4)由来の重合単位及び/又は成分(a5)由来の重合単位を含有していてもよい。緩衝層における各重合単位の含有割合は、通常、緩衝層形成用組成物を構成する各成分の比率(仕込み比)に一致する。例えば、緩衝層形成用組成物中の成分(a1)の含有量が緩衝層形成用組成物の全量(100質量部)に対して10~70質量部の場合、緩衝層は成分(a1)に由来する重合単位を10~70質量部含有する。また、緩衝層形成用組成物中の成分(a2)の含有量が緩衝層形成用組成物の全量(100質量部)に対して10~80質量部の場合、緩衝層は成分(a2)に由来する重合単位を10~80質量部含有する。成分(a3)~(a5)についても同様である。
緩衝層は、ポリオレフィン樹脂フィルムを含む層により形成されてもよい。
これらのポリオレフィン樹脂は、単独で又は2種以上を組み合わせて用いることができる。
粘着テープの表面には、剥離シートが貼付されていてもよい。剥離シートは、具体的には、粘着テープの粘着剤層の表面に貼付される。剥離シートは、粘着剤層表面に貼付されることで輸送時、保管時に粘着剤層を保護する。剥離シートは、剥離可能に粘着テープに貼付されており、粘着テープが使用される前(すなわち、ウエハ貼付前)には、粘着テープから剥離されて取り除かれる。
剥離シートは、少なくとも一方の面が剥離処理をされた剥離シートが用いられ、具体的には、剥離シート用基材の表面上に剥離剤を塗布したもの等が挙げられる。
剥離シートの厚さは、特に制限ないが、好ましくは10~200μm、より好ましくは20~150μmである。
本発明の粘着テープの製造方法としては、特に制限はなく、公知の方法により製造することができる。
例えば、基材と、当該基材の一方の面側に設けられた粘着剤層と、当該基材の他方の面側に設けられた緩衝層とを有する粘着テープの製造方法は以下のとおりである。
本発明に係る粘着テープは、好ましくは、半導体ウエハの表面に貼付してウエハの裏面研削が行う場合に使用される。より好ましくは、本発明に係る粘着テープは、ウエハの裏面研削とウエハの個片化とを同時に行うDBGにおいて好ましく使用される。特に好ましくは、本発明に係る粘着テープは、半導体ウエハを個片化した際に、カーフ幅の小さいチップ群が得られるLDBGに好ましく使用される。なお、「チップ群」とは、本発明に係る粘着テープ上に保持された、ウエハ形状に整列している複数の半導体チップをいう。
粘着テープの非限定的な使用例として、以下に半導体装置の製造方法をさらに具体的に説明する。
工程1:上記の粘着テープを半導体ウエハの表面に貼付し、粘着テープを半導体ウエハの外周に沿って切断する工程
工程2:半導体ウエハの表面側から溝を形成し、又は半導体ウエハの表面若しくは裏面から半導体ウエハ内部に改質領域を形成する工程
工程3:粘着テープが表面に貼付され、かつ上記溝又は改質領域が形成された半導体ウエハを、裏面側から研削して、溝又は改質領域を起点として、複数のチップに個片化させる工程
工程4:個片化された半導体ウエハ(すなわち、複数の半導体チップ)から、粘着テープを剥離する工程
(工程1)
工程1では、本発明の粘着テープを、粘着剤層を介して半導体ウエハ表面に貼付し、半導体ウエハの外周に沿って切断する。粘着テープは、半導体ウエハおよびその外周に拡がる外周テーブルを覆うように貼り付けられる。そして、粘着テープは、半導体ウエハの外周に沿って、カッター等により切断される。切断速度は、通常10~300mm/sである。切断時のカッター刃の温度は室温でもよく、また、カッター刃を加熱して切断してもよい。
工程2では、半導体ウエハの表面側から溝を形成し、又は半導体ウエハの表面又は裏面から半導体ウエハの内部に改質領域を形成する。
本工程で形成される溝は、半導体ウエハの厚さより浅い深さの溝である。溝の形成は、従来公知のウエハダイシング装置等を用いてダイシングにより行うことが可能である。また、半導体ウエハは、後述する工程3において、溝に沿って複数の半導体チップに分割される。
粘着テープが貼付され、かつ溝又は改質領域を形成した半導体ウエハは、チャックテーブル上に載せられ、チャックテーブルに吸着されて保持される。この際、半導体ウエハは、表面側がテーブル側に配置されて吸着される。
工程1及び工程2の後、チャックテーブル上の半導体ウエハの裏面を研削して、半導体ウエハを複数の半導体チップに個片化する。
ここで、裏面研削は、半導体ウエハに溝が形成される場合には、少なくとも溝の底部に至る位置まで半導体ウエハを薄くするように行う。この裏面研削により、溝は、ウエハを貫通する切り込みとなり、半導体ウエハは切り込みにより分割されて、個々の半導体チップに個片化される。
個片化された半導体ウエハ(すなわち、ウエハ形状に整列している複数の半導体チップ)から、粘着テープを剥離する。本工程は、例えば、以下の方法により行う。
まず、粘着テープの粘着剤層が、エネルギー線硬化性粘着剤から形成される場合には、エネルギー線を照射して粘着剤層を硬化する。次いで、個片化された半導体ウエハの裏面側に、ピックアップテープを貼付し、ピックアップが可能なように位置及び方向合わせを行う。この際、ウエハの外周側に配置したリングフレームもピックアープテープに貼り合わせ、ピックアップテープの外周縁部をリングフレームに固定する。ピックアップテープには、ウエハとリングフレームを同時に貼り合わせてもよいし、別々のタイミングで貼り合わせてもよい。次いで、ピックアップテープ上に保持された複数の半導体チップから粘着テープを剥離する。
なお、ピックアップテープは、特に限定されないが、例えば、基材と、基材の少なくとも一方の面に設けられた粘着剤層を備える粘着テープによって構成される。
基材および粘着剤層からなる半導体加工用粘着テープ(幅25mm)について、粘着剤層の一面を大気雰囲気に露出した状態で、紫外線照射装置(リンテック社製、装置名「RAD 2000」)を用いて、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を基材側から照射した。当該粘着剤層の露出した面に、23℃、50%RHにおいてPMMA板(厚さ2mm、幅70mm、長さ150mmの、三菱ケミカル株式会社製「アクリライトL001」)を2kgロールで1往復の条件で貼り付けて30分間放置した後、当該粘着テープを、測定温度25℃、剥離速度300mm/minの条件で180°剥離するときの剥離強度を測定した。同じ条件で2回測定し、その平均値を表1に示す。
粘着テープを、直径12インチ、厚み775μmのシリコンウエハにバックグラインド用テープラミネーター(リンテック社製、装置名「RAD-3510F/12」)を用いて貼付けし、シリコンウエハの外周に沿って切断した。シリコンウエハに対して、レーザーソー(ディスコ社製、装置名「DFL7361」)を用いて、波長1342nmのレーザー光をシリコンウエハの表面から照射して、シリコンウエハ内部にチップサイズが5mm×5mmとなるように改質領域を形成した。次いで、グラインダー(ディスコ社製、装置名「DGP8760」)を用いて、シリコンウエハの裏面を、研削後の厚みが30μmとなるように研削した。このとき、粘着テープは、研削後のシリコンウエハの外周を覆う大きさとなっており、シリコンウエハの外縁より1.0mm大きい大きさとなるようにした。紫外線照射装置(リンテック社製、装置名「RAD 2000」)を用いて、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を基材側、すなわちシリコンウエハの表面側から照射した。ダイシング・ダイボンディングテープ(リンテック社製、LD01D-07)の接着剤層面を、テープマウンター(リンテック社製、装置名「ADWILL RAD-2700」)を用いて60℃に加熱しながらシリコンウエハの裏面に貼付した。粘着テープを剥離した。このときの、ダイシング・ダイボンディングテープの接着剤層の剥離の程度を観察し、以下の基準で評価した。
A:剥離した面積が70%未満。
B:剥離した面積が70%以上97%未満。
C:剥離した面積が97%以上。
半導体加工用粘着テープについて、粘着剤層の一面を大気雰囲気に露出した状態で、紫外線照射装置(リンテック社製、装置名「RAD 2000」)を用いて、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を基材側から照射した。接触角計(協和界面化学株式会社製、装置名「DM-70」)を用いて、ジヨードメタン、1-ブロモナフタレン、及び蒸留水を液滴として使用し、静滴法により、JIS R 3257:1999に準拠して接触角(測定温度:25℃)を測定し、その接触角の値に基づいて北崎・畑法により、表面自由エネルギー(mJ/m2)を算出した。
半導体加工用粘着テープについて、粘着剤層の一面を大気雰囲気に露出した状態で、紫外線照射装置(リンテック社製、装置名「RAD 2000」)を用いて、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を基材側から照射した。原子間力顕微鏡(Bruker Corporation社製、装置名「Dimension Icon」)に設置した窒化ケイ素素材のカンチレバー(Bruker Corporation社製、「SCANASYST-AIR」、公称先端半径:2nm、共振周波数:70kHz、バネ定数:0.4N/m)で、室温下で、粘着剤層の表面を、押し込み量5nm、スキャン速度5Hzで押し込み、引き離しを行った。得られたフォースカーブ曲線(横軸が試料変形量であり、縦軸は測定荷重である。)について、JKR理論式とフィッテングを行い、表面弾性率を算出した。粘着剤層の表面5μm×5μm中で4096点を測定して得られる値の平均値を、表面弾性率(MPa)とした。
半導体加工用粘着テープについて、粘着剤層の一面を大気雰囲気に露出した状態で、紫外線照射装置(リンテック社製、装置名「RAD 2000」)を用いて、照度220mW/cm2および光量500mJ/cm2の条件で粘着テープに紫外線を基材側から照射した。原子間力顕微鏡(Bruker Corporation社製、装置名「Dimension Icon」)に設置した窒化ケイ素素材のカンチレバー(Bruker Corporation社製、「SCANASYST-AIR」、公称先端半径:2nm、共振周波数:70kHz、バネ定数:0.4N/m)で、室温下で、粘着剤層の表面を、押し込み量5nm、スキャン速度5Hzで押し込み、引き離しを行った。得られたフォースカーブ曲線(横軸が試料変形量であり、縦軸は測定荷重である。)について、JKR理論式とフィッテングを行い、表面弾性率を算出した。粘着剤層の表面5μm×5μm中で4096点を測定して得られる値の平均値を、凝着エネルギー(J/m2)とした。
(1)基材
基材として、両面易接着層付PETフィルム(東洋紡社製 コスモシャイン A4300、厚み:50μm、23℃におけるヤング率:2550MPa)を準備した。
(粘着剤組成物の調製)
n-ブチルアクリレート(BA)50質量部、メチルメタクリレート(MMA)20質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合して得たアクリル系重合体に、該アクリル系重合体の全水酸基のうち90モル%の水酸基に付加するように、2-メタクリロイルオキシエチルイソシアネート(MOI)を反応させて、エネルギー線硬化性のアクリル系樹脂を得た。
剥離シート(リンテック社製、商品名「SP-PET381031」)の剥離処理面に、上記で得た粘着剤組成物の塗工液を塗工し、加熱乾燥させて、剥離シート上に厚さが30μmの粘着剤層を形成した。形成した粘着剤層の表面と、基材とを貼り合わせ、半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)50質量部、メチルメタクリレート(MMA)20質量部、2-ヒドロキシエチルアクリレート(HEA)15質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)15質量部を共重合してアクリル系重合体を得た以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、エチルアクリレート(EA)60質量部、メチルメタクリレート(MMA)10質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)60質量部、メチルメタクリレート(MMA)10質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)65質量部、メチルメタクリレート(MMA)5質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、2-エチルへキシルアクリレート(2EHA)60質量部、メチルメタクリレート(MMA)10質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、2-エチルへキシルアクリレート(2EHA)40質量部、エチルアクリレート(EA)20質量部、メチルメタクリレート(MMA)10質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)30質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、エチルアクリレート(EA)60質量部、メチルメタクリレート(MMA)10質量部、2-ヒドロキシエチルアクリレート(HEA)15質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)15質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)60質量部、メチルメタクリレート(MMA)10質量部、2-ヒドロキシエチルアクリレート(HEA)15質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)15質量部を共重合してアクリル系重合体を得て、光重合開始剤としてビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキシド3.3質量部の代わりに2,2-ジメトキシ-2-フェニルアセトフェノン(IGM Resins B.V.社製、製品名「OMNIRAD 651」)2.4質量部を用いた以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)52質量部、メチルメタクリレート(MMA)20質量部、及び2-ヒドロキシエチルアクリレート(HEA)21質量部、及び2-ヒドロキシエチルメタクリレート(HEMA)7質量部を共重合してアクリル系重合体を得た以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
粘着剤組成物の調製において、n-ブチルアクリレート(BA)52質量部、メチルメタクリレート(MMA)20質量部、及び2-ヒドロキシエチルアクリレート(HEA)28質量部を共重合してアクリル系重合体を得た以外は、実施例1と同様にして半導体加工用粘着テープを作製した。
20 半導体ウエハ
30 接着テープ(ダイシング・ダイボンディングテープ)
100 本実施形態に係る粘着テープ
110 基材
120 粘着剤層
Claims (5)
- 基材と粘着剤層とを有する粘着テープであって、
前記粘着剤層の一面を大気雰囲気に露出した状態で、照度220mW/cm2および光量500mJ/cm2の条件で前記粘着テープに紫外線を照射し、当該粘着剤層の露出した面に、23℃、50%RHにおいてPMMA板を2kgロールで1往復の条件で貼り付けて30分間放置した後、当該粘着テープを180°剥離するときの剥離強度が、1600mN/25mm以下である、半導体加工用粘着テープ。 - 前記粘着剤層がアクリル系樹脂を含み、
前記アクリル系樹脂全量100質量部に対し、HEMA由来の重合単位の含有量が6質量部以上である、請求項1に記載の半導体加工用粘着テープ。 - 前記粘着剤層の一面を大気雰囲気に露出した状態で、照度220mW/cm2および光量500mJ/cm2の条件で前記粘着テープに紫外線を照射した後の、当該粘着剤層の露出した面の表面自由エネルギーが36mJ/m2未満である、請求項1または2に記載の半導体加工用粘着テープ。
- 請求項1~3のいずれかに記載の半導体加工用粘着テープを半導体ウエハの表面に貼付し、当該粘着テープを当該半導体ウエハの外周に沿って切断する工程と、
前記半導体ウエハの表面側から溝を形成し、又は前記半導体ウエハの表面若しくは裏面から半導体ウエハ内部に改質領域を形成する工程と、
前記粘着テープが表面に貼付され、かつ前記溝又は前記改質領域が形成された半導体ウエハを、裏面側から研削して、前記溝又は前記改質領域を起点として複数のチップに個片化させる工程と、
前記複数のチップから前記粘着テープを剥離する工程と、
を備える半導体装置の製造方法。 - さらに、ダイシング・ダイボンディングテープを半導体ウエハの裏面に貼付する工程を含む、請求項4に記載の半導体装置の製造方法。
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JP2020150196A (ja) * | 2019-03-15 | 2020-09-17 | 日東電工株式会社 | 接着フィルム付きダイシングテープ |
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