CN117413350A - Protective sheet for semiconductor processing and method for manufacturing semiconductor device - Google Patents
Protective sheet for semiconductor processing and method for manufacturing semiconductor device Download PDFInfo
- Publication number
- CN117413350A CN117413350A CN202280039290.3A CN202280039290A CN117413350A CN 117413350 A CN117413350 A CN 117413350A CN 202280039290 A CN202280039290 A CN 202280039290A CN 117413350 A CN117413350 A CN 117413350A
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- Prior art keywords
- wafer
- adhesive layer
- protective sheet
- semiconductor processing
- meth
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 200
- 238000012545 processing Methods 0.000 title claims abstract description 124
- 230000001681 protective effect Effects 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000012790 adhesive layer Substances 0.000 claims abstract description 187
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- 230000001070 adhesive effect Effects 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 239000010410 layer Substances 0.000 claims description 149
- 239000000463 material Substances 0.000 claims description 43
- 238000005498 polishing Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
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- 230000003068 static effect Effects 0.000 abstract description 26
- 235000012431 wafers Nutrition 0.000 description 190
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Classifications
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- 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
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- 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]
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- 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
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- 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
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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Abstract
The invention provides a protective sheet for semiconductor processing, which can restrain chip crack generated during peeling and fully restrain static generated during processing a wafer even if the wafer is thinned by DBG and the like. The protective sheet for semiconductor processing comprises: the adhesive force when the adhesive layer after energy ray curing is peeled from the silicon wafer at a peeling speed of 600 mm/min and an angle of 90 DEG between the adhesive layer and the silicon wafer is 0.035N/25mm or more and less than 0.15N/25mm.
Description
Technical Field
The present invention relates to a protective sheet for semiconductor processing and a method for manufacturing a semiconductor device. And more particularly, to a protective sheet for semiconductor processing suitable for use in a method of polishing the back surface of a wafer and singulating the wafer by using stress or the like, and a method of manufacturing a semiconductor device using the protective sheet for semiconductor processing.
Background
With the advancement of miniaturization and multifunction of various electronic devices, miniaturization and thinning of semiconductor chips mounted on these electronic devices are also demanded. To thin the chip, the back side of the semiconductor wafer is typically polished to adjust the thickness. In order to obtain a thinned chip, a method called a dicing-before-polishing method (DBG: dicing-before-polishing (Dicing Before Grinding)) is sometimes used, in which a dicing blade is used to form a trench of a predetermined depth from the front surface side of a wafer, and then polishing is performed from the back surface side of the wafer so that the polished surface reaches the trench or the vicinity of the trench, thereby singulating the wafer to obtain a chip. In DBG, since back grinding of a wafer and singulation of the wafer can be performed simultaneously, thin chips can be efficiently manufactured.
Conventionally, when a semiconductor wafer is back-polished or a chip is manufactured by DBG, an adhesive tape called a back grinding sheet is usually attached to the wafer surface in order to protect circuits on the wafer surface and to hold the semiconductor wafer and the semiconductor chip.
As an example of the back grinding sheet, patent document 1 and patent document 2 disclose a substrate having a high young's modulus and an adhesive tape having a buffer layer provided on one surface of the substrate and an adhesive layer provided on the other surface.
In recent years, as a modification of DBG, there has been proposed a method of forming a modified region in a wafer by laser light and singulating the wafer by using stress or the like at the time of polishing the back surface of the wafer. Hereinafter, this method may be referred to as LDBG (laser cutting before grinding (Laser Dicing Before Grinding)). In LDBG, since the wafer is cut in the crystal direction starting from the modified region, occurrence of chipping (chipping) can be reduced compared to DBG using a dicing blade. As a result, further thinning of the chip can be facilitated. In addition, compared to DBG in which grooves of a predetermined depth are formed on the surface of a wafer by a dicing blade, the yield of chips is excellent because there is no area where the wafer is scraped off by the dicing blade, that is, because the kerf width (kerf width) is extremely small.
Prior art literature
Patent literature
Patent document 1: international publication No. 2015/156389
Patent document 2: japanese patent application laid-open No. 2015-183008
Disclosure of Invention
Technical problem to be solved by the invention
The back grinding tape is required to be strongly bonded to the surface of the wafer when back grinding the wafer, so that circuits and the like are sufficiently protected, and to be easily peeled from the wafer when the back grinding tape is peeled from the wafer after back grinding. Therefore, the adhesive layer of the back grinding tape attached to the wafer is generally composed of an energy ray-curable adhesive. In peeling, the adhesive layer is cured by irradiation with energy rays to reduce the adhesive force, thereby achieving both the adhesion during back grinding and the peelability after back grinding.
However, if the curing of the adhesive layer by the irradiation of energy rays is insufficient, the adhesive may remain on the wafer at the time of peeling, or chips singulated due to peeling failure may come into contact with each other, and chip chipping or breakage (hereinafter, may be referred to as chip cracking) may occur. In particular, in LDBG, since the notch width of the chip is small, even a slight peeling failure may cause cracking of the chip.
In addition, static electricity is known to be generated when a wafer is processed (for example, when dicing, when back grinding, when cleaning, and when peeling back grinding tape). If static electricity is generated, chips (cut dust) generated during polishing, minute foreign matters existing in the environment, and the like are easily attached to a wafer or singulated chips.
For example, if chips, foreign matter, and the like adhere to the wafer during back grinding, the pressure during back grinding may be concentrated on the adhering foreign matter, and the wafer may be broken starting from the foreign matter, and the like. In particular, in the case of DBG for thinning and polishing a wafer, breakage of the wafer is likely to occur due to a slight pressure concentration. Therefore, it is necessary to suppress static electricity generated when processing a wafer.
When the back grinding tape described in patent document 1 and patent document 2 is used for DBG, in particular LDBG, there is a problem that the occurrence of chip cracks when peeling the back grinding tape and static electricity generated when processing wafers cannot be sufficiently suppressed.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide a protective sheet for semiconductor processing capable of suppressing occurrence of chip cracks at the time of peeling and sufficiently suppressing static electricity generated at the time of processing a wafer even when the wafer is thinned by DBG or the like, and a method for manufacturing a semiconductor device using the protective sheet for semiconductor processing.
Technical means for solving the technical problems
The scheme of the invention is as follows.
[1] A protective sheet for semiconductor processing, comprising: a base material, an antistatic layer, an energy ray curable adhesive layer and a buffer layer,
the adhesive layer after energy ray curing has an adhesive force of 0.035N/25mm or more and less than 0.15N/25mm when peeled from a silicon wafer in such a manner that the peeling speed is 600 mm/min and the angle between the adhesive layer and the silicon wafer is 90 degrees.
[2] The protective sheet for semiconductor processing according to [1], wherein the ratio of the adhesive force when the adhesive layer after the energy ray curing is peeled from the silicon wafer at a peeling speed of 600 mm/min and an angle of 90 ° with respect to the adhesive force when the adhesive layer before the energy ray curing is peeled from the silicon wafer at a peeling speed of 600 mm/min and an angle of 90 ° with respect to the adhesive layer before the energy ray curing is 4% or less.
[3]According to [1]]Or [2]]The protective sheet for semiconductor processing has a surface resistivity of 5.1X10 of the adhesive layer after curing by energy rays 12 Ω/cm 2 Above and 1.0X10 15 Ω/cm 2 The following is given.
[4] The protective sheet for semiconductor processing according to any one of [1] to [3], wherein the Young's modulus of the base material is 1000MPa or more.
[5] The protective sheet for semiconductor processing according to any one of [1] to [4], wherein the protective sheet for semiconductor processing comprises: an adhesive layer is provided on one main surface of the base material, an antistatic layer is provided between the base material and the adhesive layer, and a buffer layer is provided on the other main surface of the base material; or a structure in which an adhesive layer is provided on one main surface of a base material, and an antistatic layer and a buffer layer are provided between the base material and the adhesive layer.
[6] The protective sheet for semiconductor processing according to any one of [1] to [5], which is used in a step of polishing the back surface of a wafer having grooves formed on the front surface thereof or modified regions formed therein to singulate the wafer into chips, so as to be attached to the front surface of the wafer.
[7] A method for manufacturing a semiconductor device includes:
attaching the protective sheet for semiconductor processing described in any one of [1] to [6] to a surface of a wafer;
a step of forming a trench from the front surface side of the wafer, or a step of forming a modified region in the wafer from the front surface or the back surface of the wafer;
grinding the wafer, on the surface of which the protective sheet for semiconductor processing is attached and which is formed with grooves or modified regions, from the back side, and singulating the wafer into a plurality of chips with the grooves or modified regions as a starting point; a kind of electronic device with high-pressure air-conditioning system
And peeling the protective sheet for semiconductor processing from the singulated chips.
Effects of the invention
According to the present invention, it is possible to provide a protective sheet for semiconductor processing capable of suppressing occurrence of chip cracks at the time of peeling and sufficiently suppressing static electricity generated at the time of processing a wafer even when the wafer is thinned by DBG or the like, and a method for manufacturing a semiconductor device using the protective sheet for semiconductor processing.
Drawings
Fig. 1A is a schematic cross-sectional view showing an example of a protective sheet for semiconductor processing according to the present embodiment.
Fig. 1B is a schematic cross-sectional view showing another example of the protective sheet for semiconductor processing according to the present embodiment.
Fig. 2 is a schematic cross-sectional view showing a state in which the protective sheet for semiconductor processing according to the present embodiment is attached to the circuit surface of a wafer.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to specific embodiments using the drawings. First, main terms used in the present specification will be explained.
Singulation of a wafer refers to dividing the wafer into dies by circuits.
The "front surface" of a wafer refers to a surface on which circuits, electrodes, and the like are formed, and the "back surface" of a wafer refers to a surface on which circuits and the like are not formed.
The DBG (dicing before polishing) is a method of forming a trench of a predetermined depth on the front surface side of a wafer, polishing the wafer from the back surface side, and singulating the wafer by polishing. The grooves formed on the surface side of the wafer are formed by a method such as blade dicing, laser dicing, or plasma dicing.
In addition, LDBG (laser dicing before polishing) is a modification of DBG, and is a method of forming a modified region inside a wafer by laser light and singulating the wafer by stress or the like at the time of polishing the back surface of the wafer.
The "chip set" refers to a plurality of chips held on the protective sheet for semiconductor processing of the present embodiment after singulation of the wafer. The chips as a whole are formed in the same shape as the wafer.
(meth) acrylate "is used as a term to denote both" acrylate "and" methacrylate ", as are other similar terms.
The "energy ray" means ultraviolet rays, electron beams, or the like, and is preferably ultraviolet rays.
If not specialIn the description, the term "weight average molecular weight" refers to a polystyrene equivalent measured by Gel Permeation Chromatography (GPC). The measurement based on this method is performed, for example, in the following manner: a high-speed GPC apparatus "HLC-8120GPC" manufactured by TOSOH CORPORATION was connected with a high-speed chromatographic column "TSK guard column H XL -H”、“TSK Gel GMH XL ”、“TSK Gel G2000 H XL "(both manufactured by TOSOH CORPORATION above), at column temperature: 40 ℃ and liquid feeding speed: the detector was set to a differential refractometer at 1.0 mL/min.
(1. Protective sheet for semiconductor processing)
As shown in fig. 1A, the protective sheet 1 for semiconductor processing according to the present embodiment has a structure in which an antistatic layer 20 and an adhesive layer 30 are sequentially provided on one main surface 10a of a base material 10, and a buffer layer 40 is provided on the other main surface 10b of the base material 10. From the viewpoint of antistatic function, the antistatic layer is preferably close to the peeling interface of the protective sheet for semiconductor processing, that is, preferably close to the surface 30a of the adhesive layer. Accordingly, as shown in fig. 1A, the antistatic layer 20 is preferably provided on one principal surface 10a of the substrate 10, as compared to the other principal surface 10b of the substrate 10. When the protective sheet 1 for semiconductor processing is used, the surface 30a of the adhesive layer 30 is temporarily attached to an adherend, and then peeled off from the adherend.
The protective sheet for semiconductor processing is not limited to the configuration shown in fig. 1A. For example, as shown in fig. 1B, the protective sheet 1 for semiconductor processing may be provided with an antistatic layer 20, an adhesive layer 30, and a buffer layer 40 on one main surface 10a of the base material 10. The antistatic layer 20 and the buffer layer 40 are disposed between the substrate 10 and the adhesive layer 30. From the viewpoint of ease of manufacturing the protective sheet for semiconductor processing, as shown in fig. 1B, it is preferable that the antistatic layer 20, the buffer layer 40, and the adhesive layer 30 are disposed in this order on the base material 10. On the other hand, as described above, from the viewpoint of antistatic function, it is preferable that the buffer layer 40, the antistatic layer 20, and the adhesive layer 30 are disposed in this order on the substrate 10.
The protective sheet for semiconductor processing may have other layers as long as the effects of the present invention can be obtained. That is, if the protective sheet for semiconductor processing includes a base material, an antistatic layer, a buffer layer, and an adhesive layer, for example, another layer may be formed between the base material and the buffer layer, or another layer may be formed between the base material and the antistatic layer.
Hereinafter, a case where the protective sheet for semiconductor processing has a structure shown in fig. 1A will be described.
As shown in fig. 2, the protective sheet 1 for semiconductor processing of the present embodiment protects the surface 100a of the wafer 100 when polishing the back surface 100b of the wafer 100 by attaching the surface 30a of the adhesive layer to the surface 100a of the wafer 100, which is the circuit surface of the wafer 100 as an adherend.
As described above, when the adhesive layer after the energy ray curing has a high adhesive force, when the protective sheet for semiconductor processing is peeled from a wafer or the like, peeling failure of the adhesive layer occurs, and breakage, cracking, or the like of the wafer or the like tends to occur. In contrast, in the protective sheet for semiconductor processing according to the present embodiment, the adhesion force of the adhesive layer after the energy ray curing is set within a predetermined range, thereby reducing peeling failure of the adhesive layer.
Among them, when the amount of energy ray polymerizable carbon-carbon double bonds in the adhesive layer before curing increases, curing of the adhesive layer is easy, and the adhesive force of the adhesive layer after curing tends to be easily lowered, so that it is preferable. However, if the amount of energy ray polymerizable carbon-carbon double bonds in the adhesive layer before curing increases, the crosslinking points in the adhesive layer after curing increase, and therefore, the electric charge becomes difficult to move and further becomes easily electrostatically charged.
As is clear from this, when the wafer is processed including the back surface grinding, static electricity due to the adhesive layer is present in addition to static electricity generated by the wafer or the chipset, and therefore, it becomes difficult to alleviate the static electricity. As a result, the adhesion of foreign matter or the like to the wafer or the like due to static electricity increases, and there is a risk that the wafer or the like is damaged more. In contrast, in this embodiment, by including the antistatic layer in the protective sheet for semiconductor processing in addition to the adhesive force of the cured adhesive layer, static electricity is relaxed, and the static voltage of the wafer or the chipset is reduced.
The following describes the components of the protective sheet for semiconductor processing in detail.
(2. Substrate)
The substrate is not limited as long as it is made of a material capable of supporting the wafer before back grinding and holding the wafer after back grinding. For example, as the base material, various resin films used as a base material of the backing tape can be exemplified. The base material may be formed of a single resin film or a multilayer film formed by laminating a plurality of resin films.
(2.1 physical Properties of the substrate)
In this embodiment, the rigidity of the base material is preferably high. By making the rigidity of the base material high, vibration and the like at the time of back grinding can be suppressed, and as a result, the supporting and holding performance of the wafer and the like is improved, and breakage, cracks and the like of the wafer and the like are reduced. In addition, the stress when the protective sheet for semiconductor processing is peeled from the wafer or the like can be reduced, and breakage and cracks of the wafer or the like generated at the time of peeling can be reduced. Further, the workability in attaching the protective sheet for semiconductor processing to the wafer is also good. Specifically, the Young's modulus of the substrate at 23℃is preferably 1000MPa or more, more preferably 1800MPa or more. The upper limit of Young's modulus is not particularly limited, but is about 30000 MPa.
In this embodiment, the thickness of the base material is preferably 15 μm or more and 110 μm or less, more preferably 20 μm or more and 105 μm or less.
(2.2 materials of the substrate)
As the material of the base material, a material having a young's modulus in the above range may be selected. In this embodiment, for example, polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and wholly aromatic polyesters, polyimides, polyamides, polycarbonates, polyacetal, modified polyphenylene oxides, polyphenylene sulfides, polysulfones, polyether ketones and biaxially stretched polypropylene can be mentioned. Among them, one or more selected from polyester, polyamide, polyimide and biaxially oriented polypropylene is preferable, polyester is more preferable, and polyethylene terephthalate is still more preferable.
Further, the base material may contain a plasticizer, a lubricant, an infrared absorber, an ultraviolet absorber, a filler, a colorant, an antistatic agent, an antioxidant, a catalyst, or the like within a range not impairing the effect of the present invention. The substrate may be transparent or opaque, and may be colored or vapor deposited as needed.
In order to improve adhesion to other layers, at least one main surface of the substrate may be subjected to an adhesion treatment such as corona treatment. In addition, the substrate may have a primer layer on at least one major face.
The primer layer forming composition for forming the primer layer is not particularly limited, and examples thereof include compositions containing polyester resins, urethane resins, polyester urethane resins, acrylic resins, and the like. The primer layer-forming composition may contain a crosslinking agent, a photopolymerization initiator, an antioxidant, a softener (plasticizer), a filler, an anticorrosive agent, a pigment, a dye, and the like, as necessary.
The thickness of the primer layer is preferably 0.01 to 10. Mu.m, more preferably 0.03 to 5. Mu.m. Since the primer layer is soft, the young's modulus is less affected, and even when the primer layer is provided, the young's modulus of the base material is substantially the same as that of the resin film.
For example, the young's modulus of the substrate can be controlled by selection of the resin composition, addition of a plasticizer, stretching conditions at the time of producing a resin film, and the like.
(3. Adhesive layer)
The adhesive layer is attached to the circuit surface of the semiconductor wafer before being peeled off from the circuit surface, protects the circuit surface and supports the semiconductor wafer. In this embodiment, the adhesive layer is energy ray curable. The adhesive layer may be formed of one layer (single layer) or may be formed of a plurality of two or more layers. When the adhesive layer has a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the layers constituting the plurality of layers is not particularly limited.
The thickness of the adhesive layer is not particularly limited, but is preferably 3 μm or more and 200 μm or less, more preferably 5 μm or more and 100 μm or less. By setting the thickness of the adhesive layer within the above range, breakage of the wafer and movement of the chip can be suppressed.
The thickness of the adhesive layer refers to the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive layer.
In this embodiment, the adhesive layer has the following physical properties.
(3.1 90 ° peel adhesion of adhesive layer after energy ray curing)
In this embodiment, the adhesive layer after the energy ray curing has an adhesive force (hereinafter referred to as 90 ° peel adhesive force of the adhesive layer after the energy ray curing) of 0.035N/25mm or more and less than 0.15N/25mm when peeled from the silicon wafer so that the adhesive layer forms an angle of 90 ° with the silicon wafer. By setting the 90 ° peel adhesion of the adhesive layer after the energy ray curing within the above range, occurrence of peeling at unexpected time points before a predetermined peeling step can be suppressed, process errors (process errors) are generated, and the adhesion is sufficiently reduced, so that the adhesive layer is easily peeled from the back-ground chip set. Therefore, the residual glue on the wafer or the like, the crack of the chip, and the like can be reduced.
The 90 DEG peel adhesion of the adhesive layer after energy ray curing is preferably 0.14N/25mm or less, more preferably 0.13N/25mm or less.
In this embodiment, regarding the 90 ° peel adhesion of the adhesive layer after the energy ray curing, the adhesive layer was attached to a silicon wafer in accordance with JIS Z0237, and after the adhesive layer was cured by the energy ray, the adhesion at the peeling speed of 600 mm/min and at the angle of 90 ° at the time of peeling the cured adhesive layer from the silicon wafer was measured. Specific measurement conditions will be described in examples described later.
In addition, a peel speed of 600 mm/min tends to be faster than the conventional peel speed at which adhesion is measured. This condition assumes a peeling speed at which the adhesive layer is peeled from a wafer or the like polished by DBG or LDBG. When the peeling speed increases, the adhesion force tends to increase in general.
(3.2 ratio of 90 ° peel adhesion of adhesive layers before and after energy ray curing)
In this embodiment, the ratio of the 90 ° peel adhesion of the adhesive layer before and after the energy ray curing is preferably 4% or less. That is, the ratio of the 90 ° peel adhesion of the adhesive layer after the energy ray curing to the adhesion (hereinafter, also referred to as the ratio of the adhesion) when the adhesive layer is peeled from the silicon wafer such that the angle between the adhesive layer and the silicon wafer is 90 ° (hereinafter, also referred to as the 90 ° peel adhesion of the adhesive layer before the energy ray curing) is preferably 4% or less.
By setting the ratio of the adhesion force within the above range, the adhesive layer is sufficiently adsorbed on the surface of the wafer to protect the circuit during back grinding, and the adhesive layer is easily peeled off from the wafer or the like after back grinding, whereby cracking of the chip can be suppressed.
The ratio of the adhesion is more preferably 3% or less, and still more preferably 2% or less. On the other hand, the lower limit of the ratio of the adhesion force is not particularly limited, but is usually about 0.3%.
The 90 ° peel adhesion of the adhesive layer before the energy ray curing may be set to be the same as the method for measuring the 90 ° peel adhesion of the adhesive layer after the energy ray curing, except that the adhesive force of the adhesive layer before the energy ray curing is measured. Specific measurement conditions will be described in examples described later.
(3.3 surface resistivity)
In the present embodiment, the surface resistivity of the adhesive layer after energy ray curing is preferably 5.1X10 12 Ω/cm 2 Above and 1.0X10 15 Ω/cm 2 The following is given. The surface resistivity is the surface resistivity of the surface of the adhesive layer to which the adherend is attached (the surface 30a of the adhesive layer in fig. 1A).
The inventors of the present application found that the amount of carbon-carbon double bonds in the adhesive layer before curing affects not only the adhesion of the adhesive layer after curing but also the electrostatic properties of the adhesive layer. That is, even if the protective sheet for semiconductor processing of the present embodiment has an antistatic layer, foreign matter or the like adheres to a wafer or the like due to static electricity of the wafer or the chipset. In this case, for example, the surface resistivity of the adhesive layer is preferably set within the above range by controlling the amount of energy-ray polymerizable carbon-carbon double bonds in the adhesive layer before curing.
By setting the surface resistivity within the above range, static electricity is easily released from the protective sheet for semiconductor processing, and static electricity can be suppressed from being generated when a wafer or a chipset is processed with the protective sheet for semiconductor processing attached thereto. As a result, foreign matter or the like can be prevented from adhering to the wafer or the like in the step of adhering the protective sheet for semiconductor processing to the front surface of the wafer, the step of polishing the back surface of the wafer, the step of peeling the protective sheet for semiconductor processing, the step of transferring the wafer or the chipset after peeling the protective sheet for semiconductor processing, or the like. Therefore, breakage and cracking of the wafer or the like due to adhesion of foreign matter or the like can be suppressed.
In addition, when the surface resistivity is less than the above range, for example, curing of the adhesive layer may become insufficient. As a result, when the protective sheet for semiconductor processing is peeled off, the protective sheet may not be peeled off well from the wafer or the chip, and a part of the adhesive layer may still adhere to the wafer or the chip (residual adhesive), resulting in cracking of the chip.
The surface resistivity is more preferably 9.5X10 14 Ω/cm 2 Hereinafter, it is more preferable that the ratio is 9.0X10 14 Ω/cm 2 The following is given. On the other hand, the surface resistivity is preferably 5.2X10 12 Ω/cm 2 The above is more preferably 5.5X10 12 Ω/cm 2 The above.
In this embodiment, the surface resistivity was measured according to JIS K7194. That is, the measurement is performed in the same manner as the measurement method prescribed in JIS K7194, but the measurement conditions may be different. Specific measurement conditions will be described in examples described later.
(3.4 composition of adhesive layer)
The composition of the adhesive layer is not particularly limited as long as the adhesive layer before curing has an adhesiveness to such an extent that the circuit surface of the wafer can be protected, and the adhesive force of the adhesive layer after curing is within the above-described range. In this embodiment, the adhesive layer is preferably composed of a composition (composition for adhesive layer) containing, for example, an acrylic adhesive, a urethane adhesive, a rubber adhesive, a silicone adhesive, or the like as an adhesive component (adhesive resin) capable of exhibiting tackiness.
The composition for an adhesive layer contains an energy ray-curable adhesive from the viewpoint of facilitating the achievement of the above-mentioned ratio of the adhesive force and the adhesive force after the energy ray-curing.
(3.5 adhesive layer composition)
As described above, the adhesive layer is formed of a composition having energy ray curability (composition for adhesive layer) because it is energy ray curability. Hereinafter, the adhesive layer composition will be described.
The adhesive layer composition may have energy ray curability by blending an energy ray curable compound in addition to the adhesive resin, but the adhesive resin itself is preferably energy ray curable. When the adhesive resin itself has energy ray curability, an energy ray polymerizable group is introduced into the adhesive resin, and it is preferable to introduce the energy ray polymerizable group into the main chain or side chain of the adhesive resin.
When an energy ray-curable compound is blended in addition to the adhesive resin, a monomer or oligomer having an energy ray-polymerizable group is used as the energy ray-curable compound. The oligomer is an oligomer having a weight average molecular weight (Mw) of less than 10000, and examples thereof include urethane (meth) acrylates.
In this embodiment, from the viewpoint of controlling the amount of the energy ray polymerizable carbon-carbon double bond, it is preferably 0.1 to 300 parts by mass, more preferably 0.5 to 200 parts by mass, and even more preferably 1 to 150 parts by mass, relative to 100 parts by mass of the adhesive resin having no energy ray curability.
Hereinafter, the case where the energy ray-curable adhesive resin contained in the adhesive layer composition is an energy ray-curable acrylic polymer (hereinafter, also referred to as "acrylic polymer (a)") will be described in more detail.
(3.5.1 acrylic Polymer (A))
The acrylic polymer (a) is an acrylic polymer having an energy ray polymerizable group introduced therein and having a structural unit derived from a (meth) acrylate. The energy ray polymerizable group is preferably incorporated into a side chain of the acrylic polymer.
The acrylic polymer (a) is preferably a product obtained by reacting an acrylic copolymer (A0) with a polymerizable compound (Xa) having an energy ray polymerizable group, the acrylic copolymer (A0) having a structural unit derived from an alkyl (meth) acrylate (a 1) and a structural unit derived from a functional group-containing monomer (a 2).
As the alkyl (meth) acrylate (a 1), an alkyl (meth) acrylate having 1 to 18 carbon atoms as an alkyl group is used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, and the like are exemplified.
Among them, the alkyl (meth) acrylate (a 1) is preferably an alkyl (meth) acrylate having an alkyl group with 4 to 8 carbon atoms. Specifically, 2-ethylhexyl (meth) acrylate is preferable, n-butyl (meth) acrylate is more preferable, and n-butyl (meth) acrylate is more preferable. In addition, these alkyl (meth) acrylates may be used singly or in combination of two or more.
The content of the structural unit derived from the alkyl (meth) acrylate (a 1) in the acrylic copolymer (A0) is preferably 40 to 98% by mass, more preferably 45 to 95% by mass, and even more preferably 50 to 90% by mass, relative to the total structural units (100% by mass) of the acrylic copolymer (A0), from the viewpoint of improving the adhesive force of the adhesive layer formed.
For example, the alkyl (meth) acrylate (a 1) may contain ethyl (meth) acrylate, methyl (meth) acrylate, or the like, in addition to the above-mentioned 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate. By containing these monomers, the adhesive performance of the adhesive layer can be easily adjusted to a desired level.
The functional group-containing monomer (a 2) is a monomer having a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a cyano group, a nitrogen atom-containing ring group, or an alkoxysilyl group. Among the above, the functional group-containing monomer (a 2) is preferably one or more selected from the group consisting of a hydroxyl group-containing monomer, a carboxyl group-containing monomer and an epoxy group-containing monomer.
Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol.
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and the like.
Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates and non-acrylic epoxy group-containing monomers. Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, β -methyl glycidyl (meth) acrylate, methyl (meth) acrylate having a 3, 4-epoxycyclohexyl group, and 3-epoxycyclo-2-hydroxypropyl (meth) acrylate. Examples of the monomer containing a non-acrylic epoxy group include glycidyl crotonate and allyl glycidyl ether.
The functional group-containing monomer (a 2) may be used singly or in combination of two or more.
Among the above, the hydroxyl group-containing monomer is more preferable as the functional group-containing monomer (a 2), and among them, hydroxyalkyl (meth) acrylate is more preferable, and 2-hydroxyethyl (meth) acrylate is further preferable.
By using a hydroxyalkyl (meth) acrylate as the component (a 2), the acrylic copolymer (A0) and the polymerizable compound (Xa) can be reacted relatively easily.
The content of the structural unit derived from the functional group-containing monomer (a 2) in the acrylic copolymer (A0) is preferably 1 to 35% by mass, more preferably 3 to 32% by mass, and even more preferably 6 to 30% by mass, relative to the total structural units (100% by mass) of the acrylic copolymer (A0).
When the content is 1 mass% or more, a certain amount of functional groups as reaction points with the polymerizable compound (Xa) can be ensured. Therefore, since the adhesive layer can be appropriately cured by irradiation of energy rays, the adhesive force after irradiation of energy rays can be reduced. When the content is 30 mass% or less, a sufficient pot life (pot life) can be ensured when the adhesive layer is formed by applying a solution of the adhesive layer composition.
The acrylic copolymer (A0) may be a copolymer of the alkyl (meth) acrylate (a 1) and the functional group-containing monomer (a 2), or may be a copolymer of the component (a 1), the component (a 2) and the other monomer (a 3) other than the components (a 1) and (a 2).
Examples of the other monomer (a 3) include (meth) acrylic esters having a cyclic structure such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ethoxy (meth) acrylate, vinyl acetate, and styrene. The other monomer (a 3) may be used alone or in combination of two or more.
The content of the structural unit derived from the other monomer (a 3) in the acrylic copolymer (A0) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, relative to the total structural units (100% by mass) of the acrylic copolymer (A0).
The polymerizable compound (Xa) is a compound having an energy ray polymerizable group and a substituent (hereinafter, also simply referred to as "reactive substituent") that can react with a functional group in a structural unit of the (a 2) component derived from the acrylic copolymer (A0).
The energy ray polymerizable group may be any group containing an energy ray polymerizable carbon-carbon double bond. Examples thereof include (meth) acryl and vinyl, and (meth) acryl is preferable. The polymerizable compound (Xa) is preferably a compound having 1 to 5 energy ray polymerizable groups per molecule.
The reactive substituent in the polymerizable compound (Xa) may be appropriately changed depending on the functional group of the functional group-containing monomer (a 2), and examples thereof include an isocyanate group, a carboxyl group, and an epoxy group, and an isocyanate group is preferable from the viewpoint of reactivity and the like. When the polymerizable compound (Xa) has an isocyanate group, for example, when the functional group of the functional group-containing monomer (a 2) is a hydroxyl group, it can be easily reacted with the acrylic copolymer (A0).
Specific examples of the polymerizable compound (Xa) include (meth) acryloyloxyethyl isocyanate, 3-isopropenyl- α, α -dimethylbenzyl isocyanate, (meth) acryloylesocyanate, allyl isocyanate, glycidyl (meth) acrylate, and (meth) acrylic acid. These polymerizable compounds (Xa) may be used alone or in combination of two or more.
Among them, from the viewpoint of a compound having an appropriate isocyanate group as the reactive substituent and an appropriate distance between the main chain and the energy ray polymerizable group, a (meth) acryloyloxyethyl isocyanate is preferable.
From the viewpoint of controlling the amount of the energy ray polymerizable carbon-carbon double bond, the polymerizable compound (Xa) is preferably reacted with 50 to 98 equivalents of the functional group, more preferably 55 to 93 equivalents of the functional group, out of the total amount (100 equivalents) of the functional groups derived from the functional group-containing monomer (a 2) in the acrylic copolymer (A0).
The weight average molecular weight (Mw) of the acrylic polymer (A) is preferably 30 to 160,000,000, more preferably 40 to 140,000. By having the Mw described above, appropriate tackiness can be imparted to the adhesive layer.
Even in the case where the adhesive resin has energy ray curability, the composition for an adhesive layer preferably contains an energy ray curable compound other than the adhesive resin. As such an energy ray-curable compound, a monomer or oligomer having an unsaturated group in the molecule and being polymerization-curable by irradiation with energy rays is preferable.
Specifically, examples thereof include oligomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate, and urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and epoxy (meth) acrylate.
Among them, urethane (meth) acrylate oligomer is preferable from the viewpoint of relatively high molecular weight and surface resistivity of the adhesive layer in the above range.
The content of the energy ray-curable compound is preferably 0.1 to 300 parts by mass, more preferably 0.5 to 200 parts by mass, and even more preferably 1 to 150 parts by mass, relative to 100 parts by mass of the acrylic polymer (a) from the viewpoint of controlling the amount of the energy ray-polymerizable carbon-carbon double bond.
(3.5.2 Cross-linking agent)
The adhesive layer composition preferably further contains a crosslinking agent. For example, the composition for adhesive layer is applied and then heated, and crosslinked with a crosslinking agent. The adhesive layer can suitably form a coating film by crosslinking the acrylic polymer (a) with a crosslinking agent, and can easily function as an adhesive layer.
Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, aziridine-based crosslinking agents, and chelate-based crosslinking agents, and among these, isocyanate-based crosslinking agents are preferable. The crosslinking agent may be used alone or two or more kinds may be used in combination.
The isocyanate-based crosslinking agent may be a polyisocyanate compound. As specific examples of the polyisocyanate compound, there may be mentioned: aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate. Further, biuret and isocyanurate of the polyisocyanate compound may be mentioned, and adducts with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and castor oil may be mentioned.
Among the above, the polyol (e.g., trimethylolpropane, etc.) adducts of aromatic polyisocyanates such as toluene diisocyanate are preferred.
The content of the crosslinking agent is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, relative to 100 parts by mass of the acrylic polymer (a).
(3.5.3 photopolymerization initiator)
The adhesive layer composition preferably further contains a photopolymerization initiator. By incorporating the photopolymerization initiator in the adhesive layer composition, the adhesive layer composition can be easily cured by energy rays such as ultraviolet rays.
Examples of the photopolymerization initiator include low molecular weight { 2-methyl-1- (hydroxy-phenyl } polymerization initiators such as acetophenone, 2-diethoxybenzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, mizolone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl diphenyl sulfide, tetramethylthiuram monosulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, 1-chloroanthraquinone, 2-ethylanthraquinone, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diethylthioxanthone, isopropylthioxanthone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, and the like, and low molecular weight poly { 2-hydroxy-1- (methyl-phenyl) polymerization initiators such as 2- (2-hydroxy-phenyl) methyl-1-propanone.
The photopolymerization initiator may be used alone or in combination of two or more. Among the above, 2-dimethoxy-1, 2-diphenylethan-1-one and 1-hydroxycyclohexylphenyl ketone are preferable.
The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the acrylic polymer (a).
The composition for an adhesive layer may contain other additives within a range not impairing the effects of the present invention. Examples of the other additives include tackifiers, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, and dyes. When these additives are contained, the content of each additive is preferably 0.01 to 6 parts by mass, more preferably 0.02 to 2 parts by mass, relative to 100 parts by mass of the acrylic polymer (a).
The adhesive force of the adhesive layer can be adjusted by adjusting, for example, the kind and amount of the monomer constituting the acrylic polymer (a), the amount of the energy ray polymerizable group introduced into the acrylic polymer (a), and the like. In addition, the surface resistivity of the adhesive layer can be adjusted to some extent. In the above description, preferable ranges such as the amount of the energy ray polymerizable group introduced into the acrylic polymer (a) are described, and for example, when the amount of the energy ray polymerizable group is increased, the adhesive force after curing is lowered and the surface resistivity tends to be increased. However, the adhesion and surface resistivity of the adhesive layer may be adjusted by factors other than the above. For example, the amount of the crosslinking agent blended in the adhesive layer, the amount of the photopolymerization initiator, and the like can be appropriately adjusted.
(4. Antistatic layer)
The antistatic layer is disposed between the substrate and the adhesive layer. In the antistatic layer, the antistatic component can suppress an increase in static voltage by leakage of static electricity caused by processing or the like of the wafer to which the protective sheet for semiconductor processing is attached. The composition of the antistatic layer may be such that the stripping static voltage at the time of stripping the adhesive layer from the wafer or the like is equal to or lower than a predetermined value. In this embodiment, the stripping static voltage is preferably 500V or less.
The thickness of the antistatic layer is preferably 10nm or more, more preferably 15nm or more, further preferably 20nm or more, particularly preferably 60nm or more. Furthermore, the thickness is preferably 300nm
The wavelength is preferably 250nm or less, more preferably 200nm or less.
(4.1 antistatic layer composition)
In this embodiment, the antistatic layer is preferably composed of a composition containing a polymer compound (composition for an antistatic layer). As such a composition, a composition containing a conductive polymer compound as an antistatic component, a composition containing an antistatic component and a polymer compound, and the like can be exemplified. The composition for antistatic layer is preferably a composition containing a conductive polymer compound.
Examples of the conductive polymer compound include polythiophene-based polymer, polypyrrole-based polymer, and polyaniline-based polymer. In this embodiment, polythiophene-based polymers are preferable.
Examples of the polythiophene-based polymer include polythiophene, poly (3-alkylthiophene), poly (3-thiophene-. Beta. -ethanesulfonic acid), and a mixture (including a dopant) of polyalkylene dioxythiophene and polystyrene sulfonate (PSS). Among them, a mixture of polyalkylene dioxythiophene and polystyrene sulfonate (PSS) is preferable. The polyalkylene dioxythiophenes include poly (3, 4-ethylenedioxythiophene) (PEDOT), polypropylene dioxythiophenes, and poly (ethylene/propylene) dioxythiophenes, with poly (3, 4-ethylenedioxythiophenes) being preferred. That is, among the above, a mixture of poly (3, 4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT doped with PSS) is particularly preferable.
Examples of the polypyrrole polymer include polypyrrole, poly-3-methylpyrrole, and poly-3-octylpyrrole.
Examples of the polyaniline-based polymer include polyaniline, polymethylaniline, and polymethoxyaniline.
As the composition containing the antistatic component and the polymer compound, a composition containing the antistatic component and a binder resin is exemplified. Examples of the antistatic component include the above-mentioned conductive polymer compound, surfactant, ionic liquid, conductive inorganic compound, and the like.
The surfactant may be at least one selected from the group consisting of cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants. Cationic surfactants containing quaternary ammonium salts can be exemplified. As the conductive inorganic compound, various metals, conductive oxides, and the like can be exemplified.
In addition, the binder resin is not particularly limited. Examples thereof include polyester resins, acrylic resins, polyethylene resins, urethane resins, melamine resins, and epoxy resins. In addition, crosslinking agents may also be used simultaneously. Examples of the crosslinking agent include methylolated or alkyl-alcoholized melamine compounds, urea compounds, glyoxal compounds, acrylamide compounds, epoxy compounds, and isocyanate compounds.
The content of the antistatic agent in the composition for an antistatic layer may be appropriately determined according to the desired antistatic performance. Specifically, the content of the antistatic agent in the antistatic layer composition is preferably 0.1 to 20 mass%.
(5. Buffer layer)
As shown in fig. 1A, the buffer layer is formed on a main surface of the base material on the opposite side of the main surface on which the adhesive layer is formed. The buffer layer 40 is a softer layer than the substrate, and relieves stress during back grinding of the wafer, preventing cracking and chipping of the wafer. In addition, when the wafer to which the protective sheet for semiconductor processing is attached is subjected to back grinding, the wafer is placed on a vacuum suction table (vacuum table) with the protective sheet for semiconductor processing interposed therebetween, and the wafer is easily and properly held on the vacuum suction table by having a buffer layer as a constituent layer of the protective sheet for semiconductor processing.
Such a buffer layer is useful when processing wafers by DBG, in particular by LDBG.
The thickness of the buffer layer is preferably 5 to 100. Mu.m, more preferably 1 to 100. Mu.m, and still more preferably 5 to 80. Mu.m. By setting the thickness of the buffer layer within the above range, the stress at the time of back polishing can be appropriately relaxed by the buffer layer.
The buffer layer may be a layer formed from a composition for a buffer layer containing an energy ray polymerizable compound, or may be a film such as a polypropylene film, an ethylene-vinyl acetate copolymer film, an ionomer resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylic acid ester copolymer film, an LDPE film, or an LLDPE film.
(5.1 composition for buffer layer)
The composition for a buffer layer containing an energy ray-polymerizable compound can be cured by irradiation with energy rays.
More specifically, the composition for a buffer layer containing an energy ray-polymerizable compound preferably contains a urethane (meth) acrylate (b 1) and a polymerizable compound (b 2) having an alicyclic group or heterocyclic group having 6 to 20 ring-forming atoms. In addition to the above components (b 1) and (b 2), the composition for a buffer layer may contain a polymerizable compound (b 3) having a functional group. In addition, the composition for a buffer layer may contain a photopolymerization initiator in addition to the above components. Further, the composition for a buffer layer may contain other additives and resin components within a range that does not impair the effects of the present invention.
The components contained in the composition for a buffer layer containing an energy ray-polymerizable compound will be described in detail below.
(5.1.1 urethane (meth) acrylate (b 1))
The urethane (meth) acrylate (b 1) is a compound having at least a (meth) acryloyl group and a urethane bond, and has a property of being polymerized and cured by irradiation of energy rays. The urethane (meth) acrylate (b 1) is an oligomer or a polymer.
The weight average molecular weight (Mw) of the component (b 1) is preferably 1,000 ～ 100,000, more preferably 2,000 to 60,000, and further preferably 3,000 to 20,000. The number of (meth) acryloyl groups (hereinafter also referred to as "the number of functional groups") in the component (b 1) may be monofunctional, difunctional or trifunctional or more, but is preferably monofunctional or difunctional.
The component (b 1) can be obtained, for example, in the following manner: the method comprises the steps of reacting a polyol compound with a polyisocyanate compound to obtain a terminal isocyanate urethane prepolymer, and reacting the prepolymer with a (meth) acrylate having a hydroxyl group. The component (b 1) may be used alone or in combination of two or more.
The polyol compound as the raw material of the component (b 1) is not particularly limited as long as it is a compound having 2 or more hydroxyl groups. Any of difunctional diols, trifunctional triols, and tetrafunctional or higher polyols may be used, but difunctional diols are preferred, and polyester-type diols or polycarbonate-type diols are more preferred.
Examples of the polyisocyanate compound include: aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, dicyclohexylmethane-2, 4' -diisocyanate, and ω, ω ' -diisocyanate-dimethylcyclohexane; aromatic diisocyanates such as 4,4' -diphenylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, dimethylbiphenyl diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1, 5-diisocyanate, and the like.
Among them, isophorone diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate are preferable.
The urethane (meth) acrylate (b 1) can be obtained by reacting the above polyol compound with a polyisocyanate compound to obtain a terminal isocyanate urethane prepolymer, and reacting the prepolymer with a (meth) acrylate having a hydroxyl group. The (meth) acrylate having a hydroxyl group is not particularly limited as long as it is a compound having at least a hydroxyl group and a (meth) acryloyl group in one molecule.
Specific examples of the (meth) acrylate having a hydroxyl group include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like; hydroxy group-containing (meth) acrylamides such as N-methylol (meth) acrylamides; and a reaction product obtained by reacting a diglycidyl ester of vinyl alcohol, vinyl phenol, bisphenol A with (meth) acrylic acid.
Among them, hydroxyalkyl (meth) acrylates are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.
The content of the component (b 1) in the composition for a buffer layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 55% by mass, relative to the total amount (100% by mass) of the composition for a buffer layer.
(5.1.2 polymerizable Compound (b 2) having an alicyclic group or heterocyclic group having 6 to 20 ring-forming atoms)
The component (b 2) is a polymerizable compound having an alicyclic group or heterocyclic group having 6 to 20 ring-forming atoms, and is preferably a compound having at least one (meth) acryloyl group, more preferably a compound having one (meth) acryloyl group. By using the component (b 2), the film forming property of the obtained composition for a buffer layer can be improved.
Specific examples of the component (b 2) include: alicyclic group-containing (meth) acrylates such as isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, cyclohexyl (meth) acrylate, adamantyl (meth) acrylate, and the like; and heterocyclic group-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and morpholine (meth) acrylate (morphorine (meth) acrylate). The component (b 2) may be used alone or in combination of two or more. Among the alicyclic group-containing (meth) acrylates, isobornyl (meth) acrylate is preferred, and among the heterocyclic group-containing (meth) acrylates, tetrahydrofurfuryl (meth) acrylate is preferred.
The content of the component (b 2) in the composition for a buffer layer is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 25 to 55% by mass, relative to the total amount (100% by mass) of the composition for a buffer layer.
(5.1.3 polymerizable Compound (b 3) having functional group)
The component (b 3) is a polymerizable compound having 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, and more preferably a compound having one (meth) acryloyl group.
The component (b 3) has good compatibility with the component (b 1), and the viscosity of the composition for a buffer layer can be easily adjusted to a proper range. Further, even if the buffer layer is relatively thin, the buffer performance is good.
Examples of the component (b 3) include (meth) acrylate having a hydroxyl group, a compound having an epoxy group, a compound having an amide group, and (meth) acrylate having an amino group. Among them, (meth) acrylic esters containing hydroxyl groups are preferable.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, phenylpropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl acrylate. Among them, a hydroxyl group-containing (meth) acrylate having an aromatic ring such as phenyl hydroxypropyl (meth) acrylate is more preferable.
The component (b 3) may be used alone or in combination of two or more. In order to improve the film forming property of the composition for a buffer layer, the content of the component (b 3) in the composition for a buffer layer is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and even more preferably 10 to 30% by mass, relative to the total amount (100% by mass) of the composition for a buffer layer.
(5.1.4 polymerizable Compound (b 4) other than Components (b 1) to (b 3))
The buffer layer-forming composition may contain other polymerizable compounds (b 4) than the above-mentioned components (b 1) to (b 3) within a range that does not impair the effects of the present invention.
Examples of the component (b 4) include: alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms; vinyl compounds such as styrene, ethylene glycol vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam. The component (b 4) may be used alone or in combination of two or more.
The content of the component (b 4) in the composition for forming a buffer layer is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and particularly preferably 0 to 2% by mass.
(5.1.5 photopolymerization initiator)
The composition for a buffer layer preferably further contains a photopolymerization initiator in order to shorten the polymerization time by irradiation with energy rays and to reduce the amount of irradiation with energy rays when forming the buffer layer.
Examples of the photopolymerization initiator include benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and examples of the photopolymerization initiator include photosensitizers such as amines and quinones, and more specifically, examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, 8-chloroanthraquinone, and bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide.
These photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator in the composition for a buffer layer is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the total amount of the energy ray-polymerizable compounds.
(5.1.6 other additives)
The composition for a buffer layer may contain other additives within a range that does not impair the effects of the present invention. Examples of the other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers, rust inhibitors, pigments, and dyes. When these additives are blended, the content of each additive in the composition for a buffer layer is preferably 0.01 to 6 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the energy ray polymerizable compounds.
The buffer layer formed from the composition for a buffer layer containing an energy ray-polymerizable compound is obtained by polymerizing and curing the composition for a buffer layer having the above composition by irradiation with energy rays. That is, the buffer layer is a cured product of the composition for a buffer layer.
Therefore, the buffer layer preferably contains a polymerized unit derived from the component (b 1) and a polymerized unit derived from the component (b 2). The buffer layer may contain a polymerized unit derived from the component (b 3) or a polymerized unit derived from the component (b 4). The content ratio of each of the polymerization units in the buffer layer generally corresponds to the ratio (compounding ratio) of each of the components constituting the composition for the buffer layer.
(6. Release sheet)
A release sheet may be attached to the surface of the protective sheet for semiconductor processing. Specifically, the release sheet is attached to the surface of the adhesive layer of the protective sheet for semiconductor processing. 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 protective sheet for semiconductor processing, and is peeled from the protective sheet for semiconductor processing and removed before the protective sheet for semiconductor processing is used (i.e., before the protective sheet for semiconductor processing is attached to a wafer).
The release sheet used for the release sheet has at least one surface subjected to a release treatment, and specifically, a release sheet obtained by coating a release agent on the surface of a base material for a release sheet and the like are exemplified.
The base material for the release sheet is preferably a resin film, and examples of the resin constituting the resin film include: polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; polyolefin resins such as polypropylene resins and polyethylene resins. Examples of the release agent 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, and fluorine-based resins.
The thickness of the release sheet is not particularly limited, but is preferably 10 to 200. Mu.m, more preferably 20 to 150. Mu.m.
(7. Method for producing protective sheet for semiconductor processing)
The method for producing the protective sheet for semiconductor processing according to the present embodiment is not particularly limited as long as the antistatic layer, the buffer layer, and the adhesive layer can be formed on the main surface of the substrate, and a known method may be used. The method for manufacturing the protective sheet for semiconductor processing shown in fig. 1A will be described below.
First, as a composition for forming an antistatic layer, for example, a composition for an antistatic layer containing the above components or a composition obtained by diluting the composition for an antistatic layer with a solvent or the like is prepared. Similarly, as the adhesive layer composition for forming an adhesive layer, for example, a composition for an adhesive layer containing the above components or a composition obtained by diluting the adhesive layer composition with a solvent or the like is prepared. Similarly, as a composition for forming a buffer layer, for example, a composition for a buffer layer containing the above components or a composition obtained by diluting the composition for a buffer layer with a solvent or the like is prepared.
Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexane, n-hexane, toluene, xylene, n-propanol, and isopropanol.
Then, the composition for a buffer layer is applied to the release treated surface of the first release sheet by a known method such as spin coating, spray coating, bar coating, doctor blade coating, roll coating, blade coating, die coating, or gravure coating to form a coating film, and the coating film is semi-cured to form a buffer layer film on the release sheet. The buffer layer film formed on the release sheet is bonded to one surface of the base material, and the buffer layer film is completely cured, thereby forming a buffer layer on the base material.
In this embodiment, the curing of the coating film is preferably performed by irradiation with energy rays. The curing of the coating film may be performed by a single curing treatment or may be performed in several times.
Next, the composition for an antistatic layer is applied to the release treated surface of the second release sheet by a known method and dried by heating, thereby forming an antistatic layer on the second release sheet. Then, the antistatic layer on the second release sheet is bonded to the surface of the substrate on which the buffer layer is not formed, and the second release sheet is removed.
Next, the composition for an adhesive layer is applied to the release treated surface of the third release sheet by a known method, and is dried by heating, thereby forming an adhesive layer on the third release sheet. Then, the adhesive layer on the third release sheet is bonded to the antistatic layer on the substrate, whereby the protective sheet for semiconductor processing is obtained in which the antistatic layer and the adhesive layer are sequentially formed on one main surface of the substrate, and the buffer layer is formed on the other main surface of the substrate. The third release sheet may be removed when the protective sheet for semiconductor processing is used.
(8. Method for manufacturing semiconductor device)
In DBG, the protective sheet for semiconductor processing of the present invention is preferably applied to the surface of a semiconductor wafer and used when back grinding the wafer is performed. In particular, the protective sheet for semiconductor processing of the present invention is preferably used in LDBG which can obtain a chip set having a small kerf width when singulating semiconductor wafers.
As a non-limiting example of use of the protective sheet for semiconductor processing, a method for manufacturing a semiconductor device will be described in more detail below.
Specifically, the method for manufacturing a semiconductor device includes at least the following steps 1 to 4.
Step 1: attaching the protective sheet for semiconductor processing to a surface of a semiconductor wafer;
step 2: a step of forming a trench from the front surface side of the semiconductor wafer or a step of forming a modified region in the semiconductor wafer from the front surface or the back surface of the semiconductor wafer;
and step 3: a step of polishing a semiconductor wafer having a protective sheet for semiconductor processing attached to a surface thereof and formed with the grooves or modified regions from a back surface side, and singulating the semiconductor wafer into a plurality of chips with the grooves or modified regions as a starting point;
and 4, step 4: and a step of separating the protective sheet for semiconductor processing from the singulated semiconductor wafer (i.e., the chipset).
Each step of the method for manufacturing a semiconductor device will be described in detail below.
(Process 1)
As shown in fig. 2, in step 1, the main surface 30a of the adhesive layer 30 of the protective sheet 1 for semiconductor processing of the present embodiment is attached to the surface 100a of the semiconductor wafer 100. By attaching the protective sheet for semiconductor processing to the surface of the semiconductor wafer, the surface of the semiconductor wafer is sufficiently protected.
The present step may be performed before step 2 described later, or may be performed after step 2. For example, when forming the modified region in the semiconductor wafer, the step 1 is preferably performed before the step 2. On the other hand, when grooves are formed on the surface of the semiconductor wafer by dicing or the like, step 1 is performed after step 2. That is, in this step 1, a protective sheet for semiconductor processing is attached to the surface of a wafer having grooves formed in step 2 described later.
The semiconductor wafer used in the present manufacturing method may be a silicon wafer, or may be a wafer of gallium arsenide, silicon carbide, lithium tantalate, lithium niobate, gallium nitride, indium phosphide, or the like, or a glass wafer. In this embodiment, the semiconductor wafer is preferably a silicon wafer.
The thickness of the semiconductor wafer before polishing is not particularly limited, but is usually about 500 to 1000 μm. In addition, semiconductor wafers typically have circuits formed on their surfaces. The circuit can be formed on the wafer surface by various methods including conventional general methods such as etching and lift-off.
(Process 2)
In step 2, a trench is formed from the front surface side of the semiconductor wafer. Alternatively, the modified region is formed in the semiconductor wafer from the front surface or the back surface of the semiconductor wafer.
The trench formed in this step is a trench having a depth shallower than the thickness of the semiconductor wafer. The grooves may be formed by dicing using a conventionally known wafer dicing apparatus or the like. In step 3 described later, the semiconductor wafer is divided into a plurality of semiconductor chips along the grooves.
The modified region is an embrittled portion of the semiconductor wafer and is a region that serves as a starting point for singulation into semiconductor chips, and the semiconductor wafer is thinned by polishing in the polishing step or subjected to a force caused by polishing, whereby the modified region of the semiconductor wafer is broken and singulated into semiconductor chips. That is, the trenches and modified regions in step 2 are formed along dividing lines when the semiconductor wafer is divided and singulated into semiconductor chips in step 3 described below.
The modified region is formed by irradiating a laser beam focused on the inside of the semiconductor wafer, and the modified region is formed in the inside of the semiconductor wafer. The irradiation of the laser light may be performed from the front surface side or the back surface side of the semiconductor wafer. In the case of forming the modified region, when the step 2 is performed after the step 1 and laser irradiation is performed from the wafer surface, the semiconductor wafer is irradiated with laser light through the protective sheet for semiconductor processing.
The semiconductor wafer to which the protective sheet for semiconductor processing is attached and which is formed with the grooves or modified regions is placed on a vacuum chuck (chuck table), and is held by suction on the vacuum chuck. At this time, the semiconductor wafer is sucked so that the front surface side is arranged on the chuck side.
(step 3)
After the steps 1 and 2, the back surface of the semiconductor wafer on the vacuum chuck is polished, and the semiconductor wafer is singulated into a plurality of semiconductor chips, thereby obtaining a chip set.
Wherein, in the case of forming a trench in a semiconductor wafer, the semiconductor wafer is thinned to a position at least reaching the bottom of the trench. By this back grinding, the grooves become cuts penetrating the wafer, and the semiconductor wafer is divided by the cuts, and singulated into individual semiconductor chips.
On the other hand, in the case of forming the modified region, the polished surface (wafer back surface) may reach the modified region by polishing, but may not reach the modified region exactly. That is, the semiconductor wafer may be polished to a position close to the modified region so that the semiconductor wafer is broken from the modified region and singulated into semiconductor chips. For example, singulation of semiconductor chips can be actually performed by attaching a pickup tape described later and stretching the pickup tape.
Further, dry polishing may be performed after the back-grinding is finished and before the chip is picked up.
The semiconductor chip formed by singulation may have a square shape or an elongated shape such as a rectangular shape. The thickness of the singulated semiconductor chip is not particularly limited, but is preferably about 5 to 100 μm, and more preferably 10 to 45 μm. According to LDBG in which a modified region is provided in a wafer by laser light and the wafer is singulated by stress or the like at the time of polishing the back surface of the wafer, the thickness of singulated semiconductor chips is easily made to be 50 μm or less, more preferably 10 to 45 μm. The size of the singulated semiconductor chip is not particularly limited, but the chip size is preferably less than 600mm 2 More preferably less than 400mm 2 More preferably less than 120mm 2 。
When the protective sheet for semiconductor processing according to the present embodiment is used, even a thin and/or small semiconductor chip can be prevented from cracking during back grinding (step 3) and peeling of the protective sheet for semiconductor processing (step 4), and static electricity can be prevented.
(Process 4)
Next, the protective sheet for semiconductor processing is peeled off from the singulated semiconductor wafer (i.e., the plurality of semiconductor chips). The present step is performed, for example, by the following method.
In this embodiment, since the adhesive layer of the protective sheet for semiconductor processing is formed of an energy ray-curable adhesive, the adhesive layer is cured and shrunk by irradiation of energy rays, and the adhesion to an adherend (singulated semiconductor wafer) is reduced. Then, a pick-up tape is attached to the back surface side of the singulated semiconductor wafer, and the positions and directions are aligned so that the pick-up can be performed. At this time, the ring frame disposed on the outer peripheral side of the wafer is also bonded to the pick-up tape, and the outer peripheral edge portion of the pick-up tape is fixed to the ring frame. The pick-up tape can be attached to the wafer and the ring frame at the same time, or can be attached to the wafer and the ring frame at different times. Next, the protective sheet for semiconductor processing is peeled from the plurality of semiconductor chips held on the pickup tape.
Since the protective sheet for semiconductor processing according to the present embodiment has the above-described characteristics, even if the peeling speed is high when the protective sheet for semiconductor processing is peeled from the semiconductor wafer, no residual glue is generated on the semiconductor wafer or the like, and peeling can be performed in a state in which contact between chips is suppressed and static electricity is suppressed.
Then, a plurality of semiconductor chips on the pickup tape are picked up and fixed on a substrate or the like, thereby manufacturing a semiconductor device.
The pick-up tape is not particularly limited, and is composed of, for example, an adhesive sheet including a base material and an adhesive layer provided on one surface of the base material.
As described above, the protective sheet for semiconductor processing of the present invention has been described as an example of a method for singulating a semiconductor wafer by DBG or LDBG, but the protective sheet for semiconductor processing of the present invention can be preferably used for singulating a semiconductor wafer, and LDBG of a chip set having a small kerf width and further thinned can be obtained.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments and may be modified in various ways within the scope of the present invention.
Examples
Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
The measurement method and evaluation method in this example are as follows.
(90 ° peel adhesion of adhesive layer before and after energy ray curing)
The protective sheets for semiconductor processing produced in examples and comparative examples were cut to a width of 25mm, and the cut sheets were used as test pieces. The adhesive layer of the test piece was attached to a silicon mirror wafer on which no circuit surface was formed, using a roll having a mass of 2 kg. After leaving for 1 hour, the test piece was peeled at 90 ° relative to the silicon mirror wafer and at a peeling speed of 600 mm/min in accordance with JIS Z0237, and the adhesive force (90 ° peel adhesive force of the adhesive layer before energy ray curing) was measured.
Further, an adhesive layer of another test piece was attached to the silicon mirror wafer with a roll having a mass of 2 kg. From the substrate surface side of the protective sheet for semiconductor processing, the illuminance was 220mW/cm 2 The light quantity is 380mJ/cm 2 The adhesive layer of the test piece was irradiated with ultraviolet rays to cure the adhesive layer, and then the test piece was peeled at a peeling rate of 600 mm/min so as to be 90 ° with respect to the silicon mirror wafer in accordance with JIS Z0237, and the adhesive force (90 ° peel adhesive force of the adhesive layer after energy ray curing) was measured.
(surface resistivity of adhesive layer after energy ray curing)
The protective sheets for semiconductor processing manufactured in examples and comparative examples were cut into 10cm×10cm sizes, and the adhesive layer of the protective sheet for semiconductor processing was irradiated with ultraviolet rays to be cured. The surface resistivity of the cured adhesive layer was measured by a surface resistivity tester R8252 manufactured by ADVANTEST CORPORATION under conditions of 23 ℃ 50% rh and an applied voltage of 100V according to JIS K7194.
(stripping static Voltage of protective sheet for semiconductor processing)
The protective sheets for semiconductor processing manufactured in examples and comparative examples were attached to the surface of a silicon wafer, and the protective sheet for semiconductor processing was peeled off from the silicon wafer at a peeling speed of 600 mm/min and a temperature of 40℃using a wafer mounter (product name "RAD-2700F/12", manufactured by LINTEC Corporation), and a peeling static tester PFM-711A manufactured by Prostat was used to measure a voltage 10mm away from the surface of the wafer and the peeling surface side of the adhesive layer, and the voltage value on the wafer side was used as a peeling static voltage value. In this example, the sample having a peeling static voltage of 500V or less was judged to be good.
(crack Generation Rate)
The protective sheets for semiconductor processing produced in examples and comparative examples were attached to silicon wafers having a diameter of 12 inches and a thickness of 775 μm using a tape bonder for back grinding (manufactured by LINTEC Corporation under the apparatus name "RAD-3510F/12"). A lattice-shaped modified region was formed in the wafer using a laser cutter (manufactured by DISCO Corporation under the device name "DFL 7361"). The lattice size was 10mm×10mm.
Next, polishing (including dry polishing) was performed using a back-side polishing apparatus (DISCO Corporation, apparatus name "DGP 8761") until the thickness became 30 μm, and the wafer was singulated into a plurality of chips.
After the polishing step, energy rays (ultraviolet rays) are irradiated, and a dicing tape (manufactured by LINTEC Corporation, adwill D-175) is attached to the surface opposite to the surface to which the protective sheet for semiconductor processing is attached, and then the protective sheet for semiconductor processing is peeled off. Then, the singulated chips were observed using a digital microscope (product name "VHX-1000", manufactured by KEYENCE CORPORATION), and chips having cracks generated were counted, and the sizes of the cracks were classified according to the following criteria. The length (μm) of the crack in the longitudinal direction of the chip was compared with the length (μm) of the crack in the transverse direction of the chip, and the larger value was used as the crack size (μm).
(reference)
Large cracks: the size of the crack is more than 50 mu m
Medium crack: the crack size is 20 μm or more and 50 μm or less
Small cracks: crack size less than 20 μm
Further, the crack generation rate (%) was calculated based on the following formula. The case where the crack generation rate was 2.0% or less, the number of large cracks was 0, the number of medium cracks was 10 or less, and the number of small cracks was 20 or less was evaluated as "good", and the other cases were evaluated as "bad".
Crack generation rate (%) = (number of chips where crack was generated/total number of chips) ×100
Example 1
(1) Adhesive layer
(preparation of composition for adhesive layer)
An acrylic polymer was obtained by copolymerizing 65 parts by mass of Butyl Acrylate (BA), 20 parts by mass of Methyl Methacrylate (MMA) and 15 parts by mass of 2-hydroxyethyl acrylate (2 HEA), and the acrylic polymer was reacted with 2-methacryloyloxyethyl isocyanate (MOI) so as to add 80 mol% of hydroxyl groups to the total hydroxyl groups of the acrylic polymer, thereby obtaining an energy ray-curable acrylic resin (Mw: 50 ten thousand). To 100 parts by mass of the energy ray-curable acrylic resin, 6 parts by weight of a polyfunctional urethane acrylate (trade name: manufactured by violet ray UT-4332,Mitsubishi Chemical Corporation), 0.375 parts by mass (trade name: cornonate L) of an isocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION on a solid content basis), and 1 part by weight of a photopolymerization initiator composed of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide were added, and the mixture was diluted with a solvent to prepare a coating liquid of the composition for adhesive layer.
(formation of adhesive layer)
A release sheet (manufactured by LINTEC Corporation under the trade name "SP-PET381031", a silicone release-treated polyethylene terephthalate (PET) film, having a thickness of 38 μm) was coated with a solution of the adhesive composition and dried to prepare a release sheet with an adhesive layer having a thickness of 20. Mu.m.
(2) Production of base material with antistatic layer
As a base material, a primed PET film (TOYOBO co., ltd. Manufactured under the trade name "PET 50A-4100") having a primer layer (first primer layer) provided on one surface thereof and having a thickness of 50 μm was prepared. The Young's modulus of the PET film was 2500MPa.
A polythiophene-based conductive polymer (manufactured by Nagase ChemteX Corporation, denatron P-400 MP) was coated and dried on the surface of the PET film opposite to the surface on which the first primer layer was provided, and an antistatic layer having a thickness of 120nm was formed on the PET film.
(3) Buffer layer
(Synthesis of urethane acrylate oligomer (UA-1))
The polyester diol is reacted with isophorone diisocyanate to obtain a terminal isocyanate urethane prepolymer, and the prepolymer is reacted with 2-hydroxyethyl acrylate to obtain a difunctional urethane acrylate oligomer (UA-1) having a weight average molecular weight (Mw) of 5000.
(preparation of composition for Forming buffer layer)
A buffer layer-forming composition was prepared by blending 40 parts by mass of the above-described synthetic urethane acrylate oligomer (UA-1) as an energy ray-polymerizable compound, 40 parts by mass of isobornyl acrylate (IBXA) and 20 parts by mass of phenyl hydroxypropyl acrylate (HPPA), and further blending 2.0 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by IGM Resins corporation under the product name "OMNIRAD 184") as a photopolymerization initiator and 0.2 parts by mass of a phthalocyanine pigment.
(formation of buffer layer)
The buffer layer-forming composition was applied to a release sheet (manufactured by LINTEC Corporation under the trade name "SP-PET381031", a silicone release-treated polyethylene terephthalate (PET) film, and a thickness of 38 μm) to form a coating film. Then, the coating film was irradiated with ultraviolet rays to semi-cure the coating film, thereby forming a buffer layer forming film having a thickness of 50. Mu.m.
The ultraviolet irradiation was performed by using a conveyor type ultraviolet irradiation device (product name
"ECS-401GX", EYE GRAPHICS co., ltd., manufactured) and a high-pressure mercury lamp (H04-L41, EYE GRAPHICS co., manufactured by ltd.: H04-L41), the lamp height was 150mm, the lamp output was 3kW (converted output was 120 mW/cm), and the illuminance at 365nm of the light wavelength was 120mW/cm 2 The irradiation amount was 100mJ/cm 2 Is performed under irradiation conditions of (2).
The surface of the formed buffer layer forming film was bonded to the first primer layer of the antistatic layer-carrying base material, and ultraviolet light was again irradiated from the release sheet side on the buffer layer forming film, so that the buffer layer forming film was completely cured, thereby forming a buffer layer having a thickness of 50. Mu.m.
The ultraviolet irradiation was performed by using the ultraviolet irradiation apparatus and the high-pressure mercury lamp, and the lamp height was 150mm, the lamp output was 3kW (converted output was 120 mW/cm), and the illuminance at 365nm as the wavelength of light was 160mW/cm 2 The irradiation amount was 500mJ/cm 2 Is performed under irradiation conditions of (2).
(4) Manufacture of protective sheet for semiconductor processing
An adhesive layer of a release sheet with an adhesive layer is bonded to an antistatic layer, whereby a protective sheet for semiconductor processing is produced in which the antistatic layer and the adhesive layer are sequentially formed on one main surface of a base material, and a buffer layer is formed on the other main surface of the base material.
Example 2
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the thickness of the antistatic layer was 150nm and the thickness of the adhesive layer was 5 μm.
Example 3
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the thickness of the antistatic layer was 80nm and the thickness of the adhesive layer was 200 μm.
Example 4
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the following adhesive layer composition was used to form an adhesive layer.
(preparation of composition for adhesive layer)
89 parts by mass of n-Butyl Acrylate (BA), 8 parts by mass of Methyl Methacrylate (MMA) and 3 parts by mass of 2-hydroxyethyl acrylate (2 HEA) were copolymerized to obtain an acrylic polymer (Mw: 80 ten thousand).
For 100 parts by mass of the above-mentioned acrylic polymer, 1 part by mass (solid content) of toluene diisocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION, product name "cornonate L"), 2 parts by mass (solid content) of epoxy-based crosslinking agent (1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane), 45 parts by mass (solid content) of energy ray-curable compound (manufactured by Mitsubishi Chemical Corporation, product name "violet UV-3210 EA"), and 1 part by mass (solid content) of photopolymerization initiator (manufactured by IGM Resins corporation, product name "omnilad 184") were mixed, and diluted with a solvent to obtain a coating liquid of the composition for adhesive layer.
Example 5
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the following adhesive layer composition was used to form an adhesive layer, the thickness of the antistatic layer was set to 25nm, and the thickness of the adhesive layer was set to 5 μm.
(preparation of composition for adhesive layer)
An acrylic polymer was obtained by copolymerizing 75 parts by mass of Butyl Acrylate (BA), 20 parts by mass of Methyl Methacrylate (MMA) and 5 parts by mass of 2-hydroxyethyl acrylate (2 HEA), and the acrylic polymer was reacted with 2-methacryloyloxyethyl isocyanate (MOI) so as to add 90 mol% of the total hydroxyl groups of the acrylic polymer, thereby obtaining an energy ray-curable acrylic resin (Mw: 50 ten thousand).
To 100 parts by mass of the energy ray-curable acrylic resin, 0.375 parts by mass (based on solid content) of an isocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION, trade name: CORONATE L) and 1 part by weight of a photopolymerization initiator comprising bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide were added, and the mixture was diluted with a solvent to prepare a coating solution of the composition for an adhesive layer.
Comparative example 1
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that an antistatic layer was not provided.
Comparative example 2
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the following adhesive layer composition was used to form an adhesive layer and the thickness of the antistatic layer was set to 50 nm.
(preparation of composition for adhesive layer)
An acrylic polymer was obtained by copolymerizing 65 parts by mass of Butyl Acrylate (BA), 20 parts by mass of Methyl Methacrylate (MMA) and 15 parts by mass of 2-hydroxyethyl acrylate (2 HEA), and the acrylic polymer was reacted with 2-methacryloyloxyethyl isocyanate (MOI) so as to add 90 mol% of the total hydroxyl groups of the acrylic polymer, thereby obtaining an energy ray-curable acrylic resin (Mw: 50 ten thousand).
To 100 parts by mass of the energy ray-curable acrylic resin, 20 parts by mass of a polyfunctional urethane acrylate (trade name: manufactured by violet ray UT-4332,Mitsubishi Chemical Corporation), 0.375 parts by mass (trade name: cornonate L) of an isocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION on a solid content basis), and 1 part by mass of a photopolymerization initiator composed of bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide were added, and diluted with a solvent to prepare a coating liquid of the composition for adhesive layer.
Comparative example 3
A protective sheet for semiconductor processing was obtained in the same manner as in example 1, except that the following adhesive layer composition was used to form an adhesive layer.
(preparation of composition for adhesive layer)
An acrylic polymer was obtained by copolymerizing 75 parts by mass of Butyl Acrylate (BA), 20 parts by mass of Methyl Methacrylate (MMA) and 5 parts by mass of 2-hydroxyethyl acrylate (2 HEA), and the acrylic polymer was reacted with 2-methacryloyloxyethyl isocyanate (MOI) so as to add 50 mol% of hydroxyl groups to the total hydroxyl groups of the acrylic polymer, thereby obtaining an energy ray-curable acrylic resin (Mw: 50 ten thousand).
To 100 parts by mass of the energy ray-curable acrylic resin, 0.375 parts by mass (based on solid content) of an isocyanate-based crosslinking agent (manufactured by TOSOH CORPORATION, trade name: CORONATE L) and 1 part by weight of a photopolymerization initiator comprising bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide were added, and the mixture was diluted with a solvent to prepare a coating solution of the composition for an adhesive layer.
TABLE 1
The obtained samples (examples 1 to 5 and comparative examples 1 to 3) were subjected to the above measurement and evaluation. The ratio of the adhesion was calculated from the 90 ° peel adhesion of the adhesive layers before and after the energy ray curing. The results are shown in Table 1.
From table 1, it was confirmed that when the 90 ° peel adhesion of the adhesive layer of the protective sheet for semiconductor processing is within the above range and the antistatic layer is included in the protective sheet for semiconductor processing, the electrostatic force due to the peeling of the protective sheet for semiconductor processing is low and the crack generation rate due to the chip displacement is also low.
Description of the reference numerals
1: a protective sheet for semiconductor processing; 10: a substrate; 20: an antistatic layer; 30: an adhesive layer; 40: and a buffer layer.
Claims (7)
1. A protective sheet for semiconductor processing, comprising: a base material, an antistatic layer, an energy ray curable adhesive layer and a buffer layer,
the adhesive layer after energy ray curing has an adhesive force of 0.035N/25mm or more and less than 0.15N/25mm when peeled from a silicon wafer in such a manner that the peeling speed is 600 mm/min and the angle between the adhesive layer and the silicon wafer is 90 degrees.
2. The protective sheet for semiconductor processing according to claim 1, wherein a ratio of an adhesive force when the adhesive layer after the energy ray curing is peeled from the silicon wafer so that a peeling speed is 600 mm/min and an angle between the adhesive layer and the silicon wafer is 90 ° to an adhesive force when the adhesive layer before the energy ray curing is peeled from the wafer so that a peeling speed is 600 mm/min and an angle between the adhesive layer and the silicon wafer is 90 ° is 4% or less.
3. The protective sheet for semiconductor processing according to claim 1 or 2, wherein the surface resistivity of the adhesive layer after energy ray curing is 5.1 x 10 12 Ω/cm 2 Above and 1.0X10 15 Ω/cm 2 The following is given.
4. The protective sheet for semiconductor processing according to any one of claims 1 to 3, wherein the young's modulus of the base material is 1000MPa or more.
5. The protective sheet for semiconductor processing according to any one of claims 1 to 4, wherein the protective sheet for semiconductor processing has: the substrate has a configuration in which the adhesive layer is provided on one main surface of the substrate, the antistatic layer is provided between the substrate and the adhesive layer, and the buffer layer is provided on the other main surface of the substrate; or the adhesive layer is provided on one main surface of the base material, and the antistatic layer and the buffer layer are provided between the base material and the adhesive layer.
6. The protective sheet for semiconductor processing according to any one of claims 1 to 5, which is used in a step of polishing the back surface of a wafer having grooves formed on the front surface or modified regions formed therein to singulate the wafer into chips, and is attached to the front surface of the wafer.
7. A method for manufacturing a semiconductor device includes:
attaching the protective sheet for semiconductor processing according to any one of claims 1 to 6 to a surface of a wafer;
A step of forming a trench from the front surface side of the wafer, or a step of forming a modified region in the wafer from the front surface or the back surface of the wafer;
polishing a wafer having the protective sheet for semiconductor processing attached to a surface thereof and formed with the grooves or the modified regions from a back surface side, and singulating the wafer into a plurality of chips with the grooves or the modified regions as a starting point; a kind of electronic device with high-pressure air-conditioning system
And peeling the protective sheet for semiconductor processing from the singulated chips.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-112207 | 2021-07-06 | ||
| JP2021112207 | 2021-07-06 | ||
| PCT/JP2022/014415 WO2023281859A1 (en) | 2021-07-06 | 2022-03-25 | Protective sheet for semiconductor processing and method for producing semiconductor device |
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| CN117413350A true CN117413350A (en) | 2024-01-16 |
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| CN202280039290.3A Pending CN117413350A (en) | 2021-07-06 | 2022-03-25 | Protective sheet for semiconductor processing and method for manufacturing semiconductor device |
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| Country | Link |
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| JP (1) | JPWO2023281859A1 (en) |
| KR (1) | KR20240031949A (en) |
| CN (1) | CN117413350A (en) |
| TW (1) | TW202303742A (en) |
| WO (1) | WO2023281859A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4014283B2 (en) * | 1998-03-20 | 2007-11-28 | リンテック株式会社 | Antistatic adhesive sheet |
| JP5534896B2 (en) * | 2010-03-30 | 2014-07-02 | 古河電気工業株式会社 | Antistatic adhesive tape for semiconductor processing |
| JP5603279B2 (en) * | 2011-03-30 | 2014-10-08 | 古河電気工業株式会社 | Radiation curable adhesive tape for semiconductor processing |
| JP6322013B2 (en) | 2014-03-20 | 2018-05-09 | リンテック株式会社 | Adhesive sheet |
| TWI671379B (en) * | 2014-04-11 | 2019-09-11 | 日商琳得科股份有限公司 | Substrate for back grinding tape and back grinding tape |
| US11842916B2 (en) * | 2018-06-26 | 2023-12-12 | Lintec Corporation | Semiconductor processing adhesive tape and method of manufacturing semiconductor device |
| JP7319134B2 (en) * | 2019-08-01 | 2023-08-01 | リンテック株式会社 | Semiconductor device manufacturing method |
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2022
- 2022-03-25 CN CN202280039290.3A patent/CN117413350A/en active Pending
- 2022-03-25 KR KR1020237040010A patent/KR20240031949A/en unknown
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| WO2023281859A1 (en) | 2023-01-12 |
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