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CN110753992B - Adhesive sheet for invisible dicing and method for manufacturing semiconductor device - Google Patents

Adhesive sheet for invisible dicing and method for manufacturing semiconductor device Download PDF

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Publication number
CN110753992B
CN110753992B CN201880040196.3A CN201880040196A CN110753992B CN 110753992 B CN110753992 B CN 110753992B CN 201880040196 A CN201880040196 A CN 201880040196A CN 110753992 B CN110753992 B CN 110753992B
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China
Prior art keywords
invisible
adhesive
adhesive sheet
dicing
energy ray
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CN201880040196.3A
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CN110753992A (en
Inventor
福元孝齐
山下茂之
中村优智
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Lintec Corp
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Lintec Corp
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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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/50—Working by transmitting the laser beam through or within the workpiece
    • B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02076—Cleaning after the substrates have been singulated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H01L21/3043—Making grooves, e.g. cutting
    • 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
    • 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
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dicing (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides an adhesive sheet (1) for invisible dicing, which is at least used for cutting and separating a semiconductor wafer with a modified layer formed therein into individual chips in a room temperature environment, wherein the adhesive sheet (1) for invisible dicing is provided with a base material (11) and an adhesive layer (12) laminated on one side of the base material (11), and when the adhesive sheet (1) for invisible dicing is attached to a silicon wafer through the adhesive layer (12), the shearing force of the interface between the adhesive layer (12) and the silicon wafer at 23 ℃ is 5N/(3 mm multiplied by 20 mm) or more and 70N/(3 mm multiplied by 20 mm) or less. The adhesive sheet (1) for invisible dicing has excellent chip cleaning properties.

Description

Adhesive sheet for invisible dicing and method for manufacturing semiconductor device
Technical Field
The present invention relates to an adhesive sheet for invisible dicing (registered trademark) used for invisible dicing, and a method for manufacturing a semiconductor device using the adhesive sheet for invisible dicing.
Background
In the case of manufacturing a chip-shaped semiconductor device from a semiconductor wafer, conventionally, a blade dicing process is generally performed in which the semiconductor wafer is cut by a rotary blade while spraying a liquid for cleaning or the like to the semiconductor wafer, thereby obtaining chips. However, in recent years, invisible dicing processing capable of being divided into chips by dry dicing has been started. As an example of the invisible dicing process, a semiconductor wafer attached to a dicing sheet is irradiated with a laser having a high Numerical Aperture (NA) to minimize damage to the vicinity of the surface of the semiconductor wafer, and a modified layer is formed in advance inside the semiconductor wafer. Then, the dicing sheet is expanded to apply force to the semiconductor wafer, thereby cutting and separating the semiconductor wafer into individual chips.
In recent years, it has been demanded for the chips manufactured in the above-described manner to be stacked with another chip thereon or to be bonded to a film substrate. In some fields, flip-chip mounting or transfer of through-silicon vias (Through Silicon Via; TSVs) is performed in which a circuit of a chip is connected to a circuit of another chip or a substrate by a wire, and an electrode formation surface of the chip provided with a bump electrode is opposed to the circuit of the other chip or the substrate, and direct connection is performed by the electrode. In response to the demands for lamination and adhesion of chips in such flip chip mounting and the like, a method of fixing chips with electrodes to other chips or film substrates using an adhesive has been proposed.
In order to be easily applied to such applications, the following proposals have been made: in the above-described manufacturing method, a film-like adhesive is laminated on the electrode-forming surface of the semiconductor wafer with electrodes or the modified semiconductor wafer with electrodes, on which dicing sheets are attached on the surface opposite to the electrode-forming surface, and the chips with electrodes divided by the expanding step are provided with an adhesive layer on the electrode-forming surface. As the adhesive layer, an adhesive film called Die Attach Film (DAF) or a nonconductive adhesive film (Nonconductive film; NCF) can be used.
Patent document 1 discloses that DAF is attached to a wafer, subjected to a dicing process, and then the wafer is singulated into chips by expansion, and the DAF is divided.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-19962
Disclosure of Invention
Technical problem to be solved by the invention
However, in the above-described stealth dicing process, when the semiconductor wafer is cut and separated in the modified layer, fragments mainly derived from the modified layer may be generated, and the fragments may adhere to the chip. Thus, the chip is cleaned to remove the debris.
Such cleaning of the chips is sometimes performed on dicing sheets. That is, after dicing the semiconductor wafer into individual chips, the obtained chips are cleaned in a state of being stacked on the dicing sheet. At this time, the dicing sheet is expanded to expand the space between chips (chip space), thereby cleaning the chips more satisfactorily.
However, since the conventional dicing sheet used in the method disclosed in patent document 1 cannot be sufficiently expanded, it is difficult to sufficiently expand the chip interval and perform good cleaning.
The present invention has been made in view of the above-described circumstances, and an object thereof is to provide an adhesive sheet for dicing and a method for manufacturing a semiconductor device, which are excellent in cleaning performance of chips.
Technical means for solving the technical problems
In order to achieve the above object, in a first aspect, the present invention provides an adhesive sheet for dicing, which is used at least for cutting and separating a semiconductor wafer having a modified layer formed therein into individual chips in a room temperature environment, the adhesive sheet for dicing comprising a base material and an adhesive layer laminated on one surface side of the base material, wherein when the adhesive sheet for dicing is attached to a silicon wafer via the adhesive layer, a shearing force at an interface between the adhesive layer and the silicon wafer is 5N/(3 mm×20 mm) or more and 70N/(3 mm×20 mm) or less at 23 ℃.
By setting the shear force of the adhesive sheet for invisible-cut of the invention (1) to the above range at 23 ℃, the adhesive sheet can be satisfactorily expanded in a state in which chips are laminated. Therefore, the chip pitch can be sufficiently increased when the chips are cleaned, and as a result, the chips can be cleaned satisfactorily.
In the above invention (invention 1), the adhesive layer is preferably composed of an energy ray curable adhesive (invention 2).
In the above inventions (inventions 1 and 2), the storage modulus of the substrate at 23 ℃ is preferably 10MPa to 600MPa (invention 3).
In a second aspect, the present invention provides a method for manufacturing a semiconductor device, comprising: a bonding step of bonding the adhesive layer of the invisible-cut adhesive sheet (inventions 1 to 3) to a semiconductor wafer; a modified layer forming step of forming a modified layer inside the semiconductor wafer; an expanding step of expanding the invisible-cut adhesive sheet in a room temperature environment to cut and separate the semiconductor wafer having the modified layer formed therein into individual chips; and a cleaning step (invention 4) of cleaning the chips stacked on the invisible-dicing adhesive sheet in a state in which the invisible-dicing adhesive sheet is expanded.
In the above invention (invention 4), it is preferable that the method further comprises a lamination step of laminating an adhesive film on a surface of the semiconductor wafer bonded to the invisible-dicing adhesive sheet, the surface being opposite to the invisible-dicing adhesive sheet side (invention 5).
Effects of the invention
The present invention provides an adhesive sheet for invisible dicing and a method for manufacturing a semiconductor device, which are excellent in cleaning performance of chips.
Drawings
Fig. 1 is a plan view illustrating a method for measuring the shear force in test example 1.
FIG. 2 is a sectional view illustrating a method for measuring the shear force in test example 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
[ invisible-cutting adhesive sheet ]
The adhesive sheet for invisible dicing according to one embodiment of the present invention is used at least for cutting and separating a semiconductor wafer having a modified layer formed therein into individual chips in a room temperature environment. Here, the room temperature environment means, for example, an environment of 5 ℃ or higher, particularly preferably an environment of 10 ℃ or higher, and further preferably an environment of 15 ℃ or higher. The room temperature environment is, for example, 45℃or lower, particularly preferably 40℃or lower, and further preferably 35℃or lower. Since the above temperature ranges are easily achieved and no intentional temperature management is required, the cost of invisible dicing can be reduced. In addition, the term "sheet" in the present specification also includes the concept of "tape".
The adhesive sheet for invisible-cut of the present embodiment includes a base material and an adhesive layer laminated on one surface side of the base material. The base material and the adhesive layer are preferably laminated directly, but not limited thereto.
When the invisible-cutting adhesive sheet according to the present embodiment is attached to a silicon wafer via an adhesive layer provided in the invisible-cutting adhesive sheet, a shearing force at 23 ℃ at an interface between the adhesive layer and the silicon wafer is 5N/(3 mm. Times.20 mm) or more and 70N/(3 mm. Times.20 mm) or less.
By providing the adhesive sheet for stealth dicing according to the present embodiment with the shear force as described above, the semiconductor wafer bonded to the adhesive sheet for stealth dicing and having the modified layer formed therein can be cut and separated into individual chips by expansion in the room temperature environment, and then the chip interval can be brought into a sufficiently expanded state. Specifically, the chip spacing (the distance between the side surfaces of adjacent chips) can be increased to about 150 to 300 μm, preferably about 155 to 260 μm, and particularly preferably about 160 to 250 μm. By expanding the chip spacing to such a distance, the cleaning liquid can easily enter between the chips when cleaning the chips, and fragments generated by cutting and separating the semiconductor wafer can be effectively removed from the chips. The method for measuring the shear force is as shown in the test examples described later.
If the shear force is less than 5N/(3 mm×20 mm), when a shear force is applied to a portion where the invisible-cutting adhesive sheet and the annular frame (ring frame) are in close contact with each other during expansion, the invisible-cutting adhesive sheet is highly likely to come off from the annular frame, and therefore cannot be used stably. On the other hand, if the shear force exceeds 70N/(3 mm×20 mm), the chip spacing cannot be increased to a sufficient distance for performing good cleaning.
From the above viewpoints, the lower limit of the shearing force is preferably 10N/(3 mm. Times.20 mm) or more, particularly preferably 13N/(3 mm. Times.20 mm) or more. The upper limit of the shearing force is preferably 65N/(3 mm. Times.20 mm) or less, and particularly preferably 60N/(3 mm. Times.20 mm) or less.
In addition, the adhesive sheet for invisible-cut of the present embodiment can maintain the chip spacing at an appropriate distance even after the extended state is released. Specifically, the chip spacing after release can be maintained at about 50 to 200 μm. By maintaining the chip spacing at such a distance, the chips after release can be suppressed from colliding with each other.
1. Adhesive layer
The adhesive layer of the adhesive sheet for invisible-cut of the present embodiment is not particularly limited as long as the shear force is satisfied. The adhesive layer may be formed of a non-energy ray-curable adhesive or an energy ray-curable adhesive. The non-energy ray curable adhesive is preferably an adhesive having a desired adhesive force and re-releasability, and for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, or the like can be used. Among them, an acrylic adhesive capable of effectively suppressing the detachment of a semiconductor wafer, a chip, or the like in a modified layer forming process, an expanding process, or the like is preferable.
On the other hand, since the energy ray curable adhesive is cured by irradiation of energy rays and the adhesive force is lowered, when the chips obtained by dividing the semiconductor wafer are to be separated from the adhesive sheet for invisible dicing, the chips can be easily separated by irradiation of energy rays.
The energy ray-curable adhesive constituting the adhesive layer may contain a polymer having energy ray-curability as a main component, or may contain a mixture of a non-energy ray-curable polymer (a polymer not having energy ray-curability) and a monomer and/or oligomer having at least one or more energy ray-curable groups as a main component. The mixture of the energy ray-curable polymer and the non-energy ray-curable polymer may be a mixture of the energy ray-curable polymer and a monomer and/or oligomer having at least one or more energy ray-curable groups, or may be a mixture of the 3 kinds of substances.
First, a case where the energy ray-curable adhesive contains a polymer having energy ray-curability as a main component will be described below.
The polymer having energy ray curability is preferably a (meth) acrylate (co) polymer (a) (hereinafter, sometimes referred to as "energy ray curable polymer (a)") having a functional group having energy ray curability (energy ray curable group) introduced into a side chain. The energy ray-curable polymer (a) is preferably obtained by reacting an acrylic copolymer (a 1) having a functional group-containing monomer unit with an unsaturated group-containing compound (a 2) having a functional group bonded to the functional group. In the present specification, (meth) acrylate means both acrylate and methacrylate. Other similar terms are also the same.
The acrylic copolymer (a 1) preferably comprises: structural units derived from functional group-containing monomers; and structural units derived from (meth) acrylate monomers or derivatives thereof.
The functional group-containing monomer as the structural unit of the acrylic copolymer (a 1) is preferably a monomer having a polymerizable double bond and a functional group such as a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, or an epoxy group in the molecule.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl acrylate, and 4-hydroxybutyl (meth) acrylate, and these may be used singly or in combination of 2 or more.
Examples of the carboxyl group-containing monomer include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. These may be used alone or in combination of 2 or more.
Examples of the amino group-containing monomer or the substituted amino group-containing monomer include aminoethyl (meth) acrylate, n-butylaminoethyl (meth) acrylate, and the like. These may be used alone or in combination of 2 or more.
As the (meth) acrylic acid ester monomer constituting the acrylic copolymer (a 1), for example, a monomer having an alicyclic structure in the molecule (alicyclic structure-containing monomer) may be preferably used in addition to the alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group.
As the alkyl (meth) acrylate, particularly, alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like can be preferably used. These may be used alone or in combination of 2 or more.
As the alicyclic structure-containing monomer, for example, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like can be preferably used. These may be used alone or in combination of 2 or more.
The acrylic copolymer (a 1) preferably contains the structural unit derived from the functional group-containing monomer in an amount of 1 to 35% by mass, particularly preferably 5 to 30% by mass, and further preferably 10 to 25% by mass. The acrylic copolymer (a 1) preferably contains a structural unit derived from a (meth) acrylate monomer or a derivative thereof in an amount of 50 to 99% by mass, particularly preferably 60 to 95% by mass, and further preferably 70 to 90% by mass.
The acrylic copolymer (a 1) is obtained by copolymerizing the functional group-containing monomer described above with a (meth) acrylate monomer or a derivative thereof by a conventional method, but dimethylacrylamide, vinyl formate, vinyl acetate, styrene, or the like may be copolymerized in addition to these monomers.
The energy ray-curable polymer (a) is obtained by reacting the acrylic copolymer (a 1) having the functional group-containing monomer unit with the unsaturated group-containing compound (a 2) having a functional group bonded to the functional group.
The functional group of the unsaturated group-containing compound (a 2) may be appropriately selected depending on the kind of the functional group-containing monomer unit of the acrylic copolymer (a 1). For example, when the functional group of the acrylic copolymer (a 1) is a hydroxyl group, an amino group or a substituted amino group, the functional group of the unsaturated group-containing compound (a 2) is preferably an isocyanate group or an epoxy group, and when the functional group of the acrylic copolymer (a 1) is an epoxy group, the functional group of the unsaturated group-containing compound (a 2) is preferably an amino group, a carboxyl group or an aziridine group.
The unsaturated group-containing compound (a 2) contains at least 1, preferably 1 to 6, more preferably 1 to 4 energy ray polymerizable carbon-carbon double bonds in 1 molecule. Specific examples of the unsaturated group-containing compound (a 2) include, for example, 2-methacryloxyethyl isocyanate, m-isopropenyl- α, α -dimethylbenzyl isocyanate, methacryloyl isocyanate, allyl isocyanate, and 1,1- (bisacryloxymethyl) ethyl isocyanate; an acryl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate; an acryl monoisocyanate compound obtained by the reaction of a diisocyanate compound or polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate; glycidyl (meth) acrylate; (meth) acrylic acid, 2- (1-aziridinyl) -ethyl (meth) acrylate, 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and the like.
The unsaturated group-containing compound (a 2) is used in a proportion of preferably 50 to 95 mol%, particularly preferably 60 to 93 mol%, further preferably 70 to 90 mol%, based on the number of moles of the functional group-containing monomer of the acrylic copolymer (a 1).
In the reaction of the acrylic copolymer (a 1) and the unsaturated group-containing compound (a 2), the temperature, pressure, solvent, time, presence or absence of a catalyst, and the type of catalyst may be appropriately selected according to the combination of the functional group of the acrylic copolymer (a 1) and the functional group of the unsaturated group-containing compound (a 2). Thus, the functional group present in the acrylic copolymer (a 1) is reacted with the functional group in the unsaturated group-containing compound (a 2), and an unsaturated group is introduced into the side chain of the acrylic copolymer (a 1), thereby obtaining an energy ray-curable polymer (a).
The weight average molecular weight (Mw) of the energy ray-curable polymer (a) thus obtained is preferably 1 ten thousand or more, particularly preferably 15 ten thousand to 150 ten thousand, and further preferably 20 ten thousand to 100 ten thousand. In the present specification, the weight average molecular weight (Mw) is a standard polystyrene equivalent measured by Gel Permeation Chromatography (GPC).
Even when the energy ray-curable adhesive contains a polymer having energy ray-curability such as the energy ray-curable polymer (a) as a main component, the energy ray-curable adhesive may further contain an energy ray-curable monomer and/or oligomer (B).
As the energy ray-curable monomer and/or oligomer (B), for example, an ester of a polyol and (meth) acrylic acid or the like can be used.
Examples of the energy ray-curable monomer and/or oligomer (B) include monofunctional acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, multifunctional acrylates such as 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, polyester oligo (meth) acrylate, polyurethane oligo (meth) acrylate, and the like.
When the energy ray-curable polymer (a) is blended with the energy ray-curable monomer and/or oligomer (B), the content of the energy ray-curable monomer and/or oligomer (B) in the energy ray-curable adhesive is preferably 0.1 to 180 parts by mass, particularly preferably 60 to 150 parts by mass, per 100 parts by mass of the energy ray-curable polymer (a).
When ultraviolet rays are used as the energy rays for curing the energy ray-curable adhesive, it is preferable to add a photopolymerization initiator (C), and by using the photopolymerization initiator (C), the polymerization curing time and the light irradiation amount can be reduced.
Specific examples of the photopolymerization initiator (C) include benzophenone, acetophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal, 2, 4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzil (benzozil), dibenzoyl, diacetyl, β -chloroanthraquinone, (2, 4, 6-trimethylbenzyl diphenyl) phosphine oxide, 2-benzothiazol-N, N-diethyldithiocarbamate, oligo { 2-hydroxy-2-methyl-1- [4- (1-propenyl) phenyl ] acetone, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one. They may be used alone or in combination of 2 or more.
The photopolymerization initiator (C) is preferably used in an amount of 0.1 to 10 parts by mass, particularly preferably 0.5 to 6 parts by mass, per 100 parts by mass of the energy ray-curable polymer (a) (100 parts by mass of the total amount of the energy ray-curable copolymer (a) and the energy ray-curable monomer and/or oligomer (B) when the energy ray-curable monomer and/or oligomer (B) is blended).
In addition to the above components, other components may be blended in the energy ray curable adhesive as appropriate. Examples of the other component include a non-energy ray-curable polymer component or oligomer component (D), a crosslinking agent (E), and a polymerizable branched polymer (F).
Examples of the non-energy ray-curable polymer component or oligomer component (D) include polyacrylates, polyesters, polyurethanes, polycarbonates, polyolefins, hyperbranched polymers and the like, and polymers or oligomers having a weight average molecular weight (Mw) of 3000 to 250 ten thousand are preferable. By blending this component (D) with the energy ray-curable adhesive, the adhesiveness and peelability before curing, the strength after curing, the peelability from an adherend, the adhesiveness to other layers, the storage stability, and the like can be improved. The blending amount of the component (D) is not particularly limited, and may be appropriately determined within a range of 0.01 to 50 parts by mass based on 100 parts by mass of the energy ray curable polymer (a).
As the crosslinking agent (E), a polyfunctional compound having reactivity with a functional group of the energy ray curable polymer (a) or the like can be used. Examples of such polyfunctional compounds include isocyanate compounds, epoxy compounds, amine compounds, melamine compounds, aziridine compounds, hydrazine compounds, aldehyde compounds, oxazoline compounds, metal alkoxide compounds, metal chelate compounds, metal salts, ammonium salts, reactive phenolic resins, and the like. The shear force can be adjusted by blending the crosslinking agent (E) into the energy ray-curable adhesive.
The blending amount of the crosslinking agent (E) is preferably 0.01 to 8 parts by mass, particularly preferably 0.04 to 5 parts by mass, and further preferably 0.05 to 3.5 parts by mass, per 100 parts by mass of the energy ray curable polymer (a).
The polymerizable branched polymer (F) is a polymer having an energy ray polymerizable group and a branched structure. By incorporating the polymerizable branched polymer in the energy ray-curable adhesive, transfer of an organic substance from the adhesive layer to the semiconductor wafer or the semiconductor chip stacked on the adhesive sheet for stealth dicing can be suppressed, and mechanical load applied to the semiconductor chip can be reduced in the step of picking up the semiconductor chips from the adhesive sheet for stealth dicing, respectively. Although it has not been understood how the polymerizable branched polymer (F) contributes to such an effect, it is considered that the polymerizable branched polymer (F) tends to be easily present in the vicinity of the interface with the semiconductor wafer or the semiconductor chip in the adhesive layer, or that the polymerizable branched polymer (F) is irradiated with energy rays to polymerize with the energy ray-curable polymer (a) or the energy ray-curable monomer and/or oligomer (B), or the like.
The specific structure such as the molecular weight of the polymerizable branched polymer (F), the degree of the branched structure, and the number of the energy ray polymerizable groups in one molecule is not particularly limited. As an example of a method for obtaining such a polymerizable branched polymer (F), first, a monomer having 2 or more radical polymerizable double bonds in the molecule, a monomer having an active hydrogen group and 1 radical polymerizable double bond in the molecule, and a monomer having 1 radical polymerizable double bond in the molecule are polymerized, thereby obtaining a polymer having a branched structure. Then, the obtained polymer is reacted with a compound having a functional group capable of reacting with an active hydrogen group of the polymer to form a bond and at least 1 radical polymerizable double bond in a molecule, thereby obtaining a polymerizable branched polymer (F). As a commercial product of the polymerizable branched polymer (F), for example, "OD-007" manufactured by Nissan Chemical Industries, ltd.
The weight average molecular weight (Mw) of the polymerizable branched polymer (F) is preferably 1000 or more, particularly preferably 3000 or more, from the viewpoint of easily and moderately suppressing the interaction between the energy ray-curable polymer (a) and the energy ray-curable monomer and/or oligomer (B). The weight average molecular weight (Mw) is preferably 100,000 or less, and particularly preferably 30,000 or less.
The content of the polymerizable branched polymer (F) in the adhesive layer is not particularly limited, but is usually preferably 0.01 parts by mass or more, and preferably 0.1 parts by mass or more, based on 100 parts by mass of the energy ray curable polymer (a), from the viewpoint of favorably obtaining the above-described effects by containing the polymerizable branched polymer (F). Since the polymerizable branched polymer (F) has a branched structure, the above-described effects can be obtained well even if the content in the adhesive layer is a relatively small amount.
Depending on the type of the polymerizable branched polymer (F), the polymerizable branched polymer (F) may remain in the form of particles on the contact surface of the semiconductor wafer or the semiconductor chip with the adhesive layer. Since the particles may lower the reliability of the product having the semiconductor chip, the number of particles remaining is preferably small. Specifically, the number of particles having a particle diameter of 0.20 μm or more remaining on a silicon wafer as a semiconductor wafer is preferably less than 100, and particularly preferably 50 or less. From the viewpoint of easily satisfying such a demand for particles, the content of the polymerizable branched polymer (F) is preferably less than 3.0 parts by mass, particularly preferably 2.5 parts by mass or less, and further preferably 2.0 parts by mass or less, per 100 parts by mass of the energy ray curable polymer (a).
Next, a case where the energy ray curable adhesive contains a mixture of a non-energy ray curable polymer component and a monomer and/or oligomer having at least one or more energy ray curable groups as a main component will be described below.
As the non-energy ray-curable polymer component, for example, the same component as the acrylic copolymer (a 1) can be used.
The monomer and/or oligomer having at least one energy ray-curable group may be the same as the component (B). The blending ratio of the non-energy ray-curable polymer component and the monomer and/or oligomer having at least one energy ray-curable group is preferably 1 to 200 parts by mass, particularly preferably 60 to 160 parts by mass, relative to 100 parts by mass of the non-energy ray-curable polymer component.
In this case, the photopolymerization initiator (C) or the crosslinking agent (E) may be blended as appropriate in the same manner as described above.
The thickness of the adhesive layer is not particularly limited as long as the adhesive layer can function properly in each step of using the adhesive sheet for invisible-cut of the present embodiment. Specifically, it is preferably 1 to 50. Mu.m, particularly preferably 3 to 40. Mu.m, and further preferably 5 to 30. Mu.m.
The adhesive layer in the adhesive sheet for invisible-cutting according to the present embodiment preferably has a storage modulus at 23℃of 1 to 5000kPa, particularly preferably 3 to 3000kPa, and further preferably 5 to 2500kPa. By setting the storage modulus of the adhesive layer at 23 ℃ to the above range, the adhesive sheet for dicing can be easily expanded, the chip interval can be easily and effectively expanded, and the chips can be cleaned more favorably. The method for measuring the storage modulus is as described in the test examples described later.
2. Substrate material
The storage modulus of the base material in the adhesive sheet for invisible cutting according to the present embodiment is preferably 10MPa or more and 600MPa or less at 23 ℃. When the shear force of the adhesive layer is within the above range, the storage modulus of the base material is also within the above range, and the chip interval of the chips attached to the invisible-dicing adhesive sheet can be further sufficiently increased by the synergistic effect of these, and the chips can be effectively cleaned. The method for measuring the storage modulus is as described in the test examples described later.
Further, since the base material exhibits a predetermined rigidity when the storage modulus is 10MPa or more, the adhesive layer formed on the release sheet or the like can be laminated on the base material by transfer printing, and the adhesive sheet for invisible-cut can be efficiently produced. Further, the adhesive sheet for invisible-cut is also excellent in handleability. On the other hand, when the storage modulus is 600MPa or less, the adhesive sheet for invisible cutting is stretched well by expansion. In addition, the semiconductor wafer can be well supported by the invisible-cut adhesive sheet attached to the annular frame.
From the above point of view, the lower limit value of the storage modulus is more preferably 50MPa or more, and particularly preferably 100MPa or more. The upper limit of the storage modulus is more preferably 580MPa or less, and particularly preferably 550MPa or less.
When a modified layer forming step of irradiating a semiconductor wafer bonded to the invisible-dicing adhesive sheet with laser light through the invisible-dicing adhesive sheet is performed, it is preferable that the base material in the invisible-dicing adhesive sheet of the present embodiment exhibits excellent light transmittance to light of the wavelength of the laser light.
In the case of curing the adhesive layer by using energy rays, the base material preferably has light transmittance to the energy rays. The energy rays are described later.
The base material of the adhesive sheet for invisible-cutting according to the present embodiment preferably includes a film (resin film) mainly composed of a resin-based material, and particularly preferably is formed only of a resin film. Specific examples of the resin film include an ethylene-vinyl acetate copolymer film; ethylene copolymer films such as ethylene- (meth) acrylic acid copolymer films, ethylene- (meth) acrylic acid methyl ester copolymer films, and other ethylene- (meth) acrylic acid ester copolymer films; polyolefin films such as polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, and norbornene resin film; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; polyester films such as polyethylene terephthalate films, polybutylene terephthalate films, and polyethylene naphthalate films; (meth) acrylate copolymer films; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; a fluororesin film, and the like. Examples of the polyethylene film include a Low Density Polyethylene (LDPE) film, a Linear Low Density Polyethylene (LLDPE) film, and a High Density Polyethylene (HDPE) film. In addition, modified membranes such as crosslinked membranes, ionomer membranes, and the like of the above membranes may also be used. The substrate may be a film formed of 1 of the above materials, or may be a film formed of a combination of 2 or more of the above materials. The laminated film may have a multilayer structure in which a plurality of layers made of 1 or more materials described above are laminated. In the laminated film, the materials constituting the respective layers may be the same or different.
Among the above films, polyolefin-based films such as ethylene-methacrylic acid copolymer films, polyethylene films, and polypropylene films, ionomer films of such polyolefin, polyvinyl chloride-based films, polyurethane films, or (meth) acrylic acid ester copolymer films, films made of linear low density polyethylene and polypropylene, and the like are preferably used.
The base material may contain various additives such as a filler, a flame retardant, a plasticizer, an antistatic agent, a lubricant, an antioxidant, a colorant, an infrared absorber, an ultraviolet absorber, and an ion scavenger in the film. The content of these additives is not particularly limited, but is preferably set in a range where the base material exhibits a desired function.
In the adhesive sheet for invisible-cut of the present embodiment, when the base material and the adhesive layer are directly laminated, a surface treatment such as primer treatment (primer), corona treatment, or plasma treatment may be applied to the surface of the base material on the adhesive layer side in order to improve the adhesion to the adhesive layer.
The thickness of the base material is not limited as long as it can function properly in the step of using the adhesive sheet for invisible dicing. The thickness is usually preferably 20 to 450. Mu.m, particularly preferably 25 to 250. Mu.m, and further preferably 50 to 150. Mu.m.
3. Stripping sheet
In order to protect the adhesive layer until the adhesive sheet for invisible-cut is used, a release sheet may be laminated on the surface of the adhesive layer for invisible-cut of the present embodiment opposite to the substrate side.
The release sheet is not particularly limited, and for example, a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate film, an ionomer resin film, an ethylene- (meth) acrylic acid copolymer film, an ethylene- (meth) acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like can be used. In addition, crosslinked films of the above films may also be used. Further, a laminated film may be formed by laminating a plurality of the above films.
The release surface (surface having releasability; particularly, surface in contact with the adhesive layer) of the release sheet is preferably subjected to a release treatment. Examples of the release agent used for the release treatment include release agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax.
The thickness of the release sheet is not particularly limited, but is usually about 20 μm to 100 μm.
4. Adhesive force
The adhesive sheet for invisible-cut of the present embodiment preferably has an adhesive force to a mirror silicon wafer (silicon mirror wafer) at 23℃of 1N/25mm or more, particularly preferably 2N/25mm or more. The adhesion is preferably 30N/25mm or less, and particularly preferably 29.5N/25mm or less. When the adhesive force at 23 ℃ is set to the above range, the predetermined position of the semiconductor wafer or the obtained semiconductor chip can be easily maintained when the adhesive sheet is expanded in the expansion step, and the division of the modified layer portion of the semiconductor wafer can be satisfactorily performed. When the adhesive layer is made of an energy ray-curable adhesive, the adhesive force refers to an adhesive force before irradiation with energy rays. The adhesive force is a force measured by a method described later.
In the adhesive sheet for invisible-cut of the present embodiment, when the adhesive layer is made of an energy ray-curable adhesive, the adhesion to the silicon mirror wafer after irradiation with energy rays at 23 ℃ is preferably 10mN/25mm or more, and particularly preferably 20mN/25mm or more. The adhesion is preferably 1000mN/25mm or less, and particularly preferably 900mN/25mm or less. After the singulation of the semiconductor wafer is completed, the adhesive sheet for stealth dicing can be irradiated with energy rays to reduce the adhesive force to the above-described range, whereby the resulting semiconductor chips can be easily picked up. The adhesion force is a force measured by a method described later.
The above-mentioned adhesive force at 23℃and adhesive force after irradiation with energy rays at 23℃can be measured by the following methods. First, a semiconductor processing sheet was cut to a width of 25mm, and the adhesive layer side surface thereof was attached to a silicon mirror wafer. The application was performed using a laminator (manufactured by LINTEC CORPORATION under the product name "RAD-3510F/12") at an application speed of 10mm/s, a wafer protrusion amount of 20 μm and a roll pressure of 0.1 MPa. Next, the obtained laminate of the semiconductor wafer and the silicon mirror wafer was placed under an atmosphere of 50% rh at 23 ℃ for 20 minutes. Here, when the adhesion after irradiation with energy rays at 23℃was measured, the laminate was subjected to Ultraviolet (UV) irradiation (illuminance: 230 mW/cm) from the substrate side of the sheet under a nitrogen atmosphere using an ultraviolet irradiation apparatus (manufactured by LINTEC CORPORATION under the product name "RAD-2000 m/12") after 20 minutes of standing 2 Light, lightThe amount was 190mJ/cm 2 ). After leaving for 20 minutes or UV irradiation, the sheet was peeled from the silicon mirror wafer at a peeling angle of 180℃and a peeling speed of 300mm/min in accordance with JIS Z0237 using a universal tensile tester (Advanced Micro Devices, manufactured by Inc., product name "RTG-1225"), and the measured value was regarded as an adhesive force (mN/25 mm).
5. Method for manufacturing adhesive sheet for invisible cutting
The method for producing the invisible-cutting adhesive sheet according to the present embodiment is not particularly limited, and a conventional method can be used. As a first example of the production method, first, an adhesive composition containing a material of the adhesive layer and a coating composition further containing a solvent or a dispersion medium as required are prepared. Next, the coating composition is applied to the release surface of the release sheet using a die coater, curtain coater, spray coater, slot coater, blade coater, or the like, to form a coating film. Further, by drying the coating film, an adhesive layer is formed. Then, the adhesive layer on the release sheet and the base material are bonded to obtain an adhesive sheet for invisible dicing. The properties of the coating composition are not particularly limited as long as the coating composition can be applied. The component for forming the adhesive layer may be contained as a solute in the coating composition or as a dispersion medium.
When the coating composition contains the crosslinking agent (E), the drying conditions (temperature, time, etc.) may be changed or a heat treatment may be additionally provided in order to form a crosslinked structure at a desired existing density. In order to sufficiently perform the crosslinking reaction, the adhesive layer is generally laminated on the base material by the above-mentioned method or the like, and then the obtained adhesive sheet for invisible-cut is cured by standing for several days in an environment of, for example, 23 ℃ and 50% relative humidity.
As a second example of the method for producing the invisible-cut adhesive sheet according to the present embodiment, first, the coating composition is applied to one surface of a substrate to form a coating film. Subsequently, the coating film is dried to form a laminate of the substrate and the adhesive layer. Further, an exposed surface of the adhesive layer in the laminate and a release surface of the release sheet are bonded. Thus, an adhesive sheet for invisible-cut that has a release sheet laminated on an adhesive layer can be obtained.
[ method for manufacturing semiconductor device ]
The method for manufacturing a semiconductor device according to one embodiment of the present invention includes the steps of: a bonding step of bonding the adhesive layer of the invisible-cut adhesive sheet (invisible-cut adhesive sheet of the present embodiment) to a semiconductor wafer; a modified layer forming step of forming a modified layer inside the semiconductor wafer; an expanding step of expanding the invisible dicing adhesive sheet in a room temperature environment to cut and separate the semiconductor wafer having the modified layer formed therein into individual chips; and a cleaning step of cleaning the chips stacked on the invisible-dicing adhesive sheet in a state in which the invisible-dicing adhesive sheet is expanded.
In the above-described production method, the bonding step may be performed before the modified layer forming step, or conversely, the modified layer forming step may be performed before the bonding step. In the former case, the modified layer forming step irradiates the semiconductor wafer bonded to the adhesive sheet for invisible dicing of the present embodiment with laser light. In the latter case, for example, a semiconductor wafer bonded to another adhesive sheet (for example, a back surface polishing sheet) is irradiated with laser light.
According to the method for manufacturing a semiconductor device of the present embodiment, since the invisible-cut adhesive sheet is used at least in the cleaning step, the distance between chips can be sufficiently increased by expanding the invisible-cut adhesive sheet. Therefore, the cleaning liquid easily enters between the chips, and good chip cleaning can be performed.
The method for manufacturing a semiconductor device according to the present embodiment may further include a lamination step of laminating an adhesive film (DAF, NCF, etc.) on a surface of the semiconductor wafer bonded to the adhesive sheet for dicing in a state opposite to the adhesive sheet for dicing in a state of being invisible. According to the method for manufacturing a semiconductor device of the present embodiment, the adhesive film can be divided satisfactorily by the expanding step.
Hereinafter, a preferred specific example of a method for manufacturing a semiconductor device according to an embodiment of the present invention will be described.
(1) Bonding step
First, a bonding step of bonding the adhesive layer of the invisible-cut adhesive sheet according to the present embodiment to a semiconductor wafer is performed. In general, the surface of the invisible-cut adhesive sheet on the adhesive layer side is placed (mount) on one surface of a semiconductor wafer, but the present invention is not limited thereto. In this bonding step, a ring-shaped frame is generally attached to the outer peripheral side region of the region to which the semiconductor wafer is attached, of the surface of the adhesive layer side of the invisible dicing adhesive sheet. At this time, in a plan view, a region where the adhesive layer is exposed exists as a peripheral region between the ring frame and the semiconductor wafer.
(2) Lamination process
Next, a lamination step of laminating an adhesive film on a surface of the semiconductor wafer bonded to the adhesive sheet for dicing opposite to the adhesive sheet for dicing may be performed. The lamination is typically performed by heat lamination (thermal lamination). When the semiconductor wafer has an electrode on the surface, the electrode is usually present on the surface of the semiconductor wafer opposite to the side of the invisible-cut adhesive sheet, and therefore the adhesive film is laminated on the electrode side of the semiconductor wafer.
The adhesive film may be any of DAF and NCF, and generally has heat-sensitive adhesive properties. The material is not particularly limited, and specific examples thereof include a film-like member formed of an adhesive composition containing a heat-resistant resin material such as a polyimide resin, an epoxy resin, a phenolic resin, and a curing accelerator.
(3) Modified layer Forming Process
The step of forming the modified layer in the semiconductor wafer is preferably performed after the bonding step or after the lamination step, but the step of forming the modified layer may be performed before these steps. In general, the modified layer forming step is performed by irradiating a laser beam (invisible dicing) in an infrared region so as to focus on a focal point set in the semiconductor wafer. The irradiation of the laser light may be performed from any side of the semiconductor wafer. When the modified layer forming step is performed after the laminating step, it is preferable to irradiate the laser beam through the invisible-cut adhesive sheet. In the case where the modified layer forming step is performed between the bonding step and the laminating step, or in the case where the laminating step is not performed, it is preferable that the laser beam is directly irradiated to the semiconductor wafer without passing through the invisible-cut adhesive sheet.
(4) Expansion process
After the modified layer forming step, the invisible dicing adhesive sheet is expanded in a room temperature environment, whereby an expansion step of cutting and separating the semiconductor wafer is performed. In this way, the semiconductor chips formed by dividing the semiconductor wafer are attached to the adhesive layer of the invisible-cut adhesive sheet. When an adhesive film is laminated on a semiconductor wafer, the adhesive film is also divided by an expanding process to divide the semiconductor wafer and to obtain chips with an adhesive layer.
The specific conditions in the expansion step are not limited. For example, the temperature at which the adhesive sheet for invisible cutting is spread may be a general spreading temperature, and as described above, it is usually 5 ℃ or higher, particularly preferably 10 ℃ or higher, and further preferably 15 ℃ or higher. The temperature is usually 45℃or lower, particularly 40℃or lower, and more particularly 35℃or lower.
(5) Cleaning process
After the expansion step, a cleaning step of cleaning the chips stacked on the invisible-dicing adhesive sheet is performed in a state in which the invisible-dicing adhesive sheet is expanded. The expansion in the cleaning step may be performed under normal conditions, and for example, the expansion performed in the expansion step may be used in the cleaning step as it is, or the adhesive sheet for invisible cutting may be expanded again after the expansion step is released for the cleaning step. The cleaning may be performed under normal conditions, and for example, the adhesive sheet for dicing may be immersed in a cleaning liquid together with the chip. As described above, by performing the cleaning step using the adhesive sheet for invisible dicing according to the present embodiment, the obtained chip spacing can be sufficiently widened, and thus, the chips adhering to the chips can be removed satisfactorily. The cleaning step may be performed after the shrinkage step described below.
(6) Shrinkage process
When the peripheral edge region of the adhesive sheet for invisible-cut (the region between the ring-shaped frame and the chip set when viewed from above) is loosened by the expansion step, it is preferable to perform a contraction step of heating the peripheral edge region. By heating the peripheral edge region of the invisible-cutting adhesive sheet, the base material located in the peripheral edge region is shrunk, and the amount of loosening of the invisible-cutting adhesive sheet generated in the expansion step can be reduced. The heating method in the shrinking step is not limited. Hot air can be blown, infrared rays can be irradiated, and microwaves can also be irradiated.
(7) Pick-up process
In the case where the shrink process is performed after the cleaning process, the pick-up process is performed after the shrink process, and in the case where the cleaning process is performed after the shrink process or the case where the shrink process is not performed, the pick-up process is performed after the cleaning process, in which chips attached to the invisible-dicing adhesive sheet are picked up from the invisible-dicing adhesive sheet, respectively, to obtain chips as semiconductor devices.
Here, when the adhesive layer of the invisible-cut adhesive sheet is formed of an energy ray-curable adhesive, it is preferable that the adhesive layer is irradiated with energy rays at any stage after the bonding step and before the picking up step to cure the adhesive layer, thereby reducing the adhesive force. Thereby, the above-described pickup of the chip can be performed more easily.
The energy rays include ionizing radiation, that is, X-rays, ultraviolet rays, electron beams, and the like. Among them, ultraviolet rays which are relatively easy to introduce by irradiation equipment are preferable.
When ultraviolet rays are used as the ionizing radiation, near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380nm may be used in terms of ease of handling. The amount of ultraviolet light is appropriately selected depending on the type of the energy ray-curable adhesive contained in the adhesive layer or the thickness of the adhesive layer, and is usually 50 to 500mJ/cm 2 About, preferably 100 to 450mJ/cm 2 More preferably 150 to 400mJ/cm 2 . In addition, the ultraviolet illuminance is usually 50 to 500mW/cm 2 About, preferably 100 to 450mW/cm 2 More preferably 150 to 400mW/cm 2 . The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a halogen lamp, a Light Emitting Diode (LED), or the like may be used.
When an electron beam is used as the ionizing radiation, the acceleration voltage is preferably about 10 to 1000kV, as long as it is appropriately selected depending on the type of the energy ray polymerizable group or the energy ray polymerizable compound contained in the adhesive layer or the thickness of the adhesive layer. The irradiation amount may be appropriately selected according to the type of the energy ray curable adhesive contained in the adhesive layer or the thickness of the adhesive layer, and is usually selected in the range of 10 to 1000 rad. The electron beam source is not particularly limited, and various electron beam accelerators of the type of kokk Rao Fu-Walton (Cockcroft-Walton), vandaf (van de graaff), resonant transformer, insulating core transformer, linear type, denafil (dynamoton) type, high frequency type, and the like can be used, for example.
By performing the above-described manufacturing method, a semiconductor device can be manufactured using the adhesive sheet for invisible-cut of the present embodiment.
The embodiments described above are described for easy understanding of the present invention, and are not described for limiting the present invention. Accordingly, the elements disclosed in the above embodiments also cover all design changes and equivalents that fall within the technical scope of the present invention.
Examples
The present invention will be further specifically described with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
(1) Preparation of adhesive composition
Butyl acrylate/methyl methacrylate/2-hydroxyethyl acrylate=80/5/15 (mass ratio) to obtain an acrylic copolymer, and reacting the acrylic copolymer with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to the 2-hydroxyethyl acrylate to obtain an energy ray-curable polymer. The weight average molecular weight (Mw) of the energy ray-curable polymer was 40 ten thousand.
100 parts by mass (calculated as solids; hereinafter described in the same manner) of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (product name "Irgacure184" manufactured by Basv corporation) as a photopolymerization initiator, and 0.49 parts by mass of toluene diisocyanate-based crosslinking agent (Nippon Polyurethane Industry Co., ltd., product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition.
(2) Manufacturing of adhesive sheet for invisible cutting
The adhesive composition was applied to the release surface of a release sheet (manufactured by LINTEC CORPORATION under the product name "SP-PET 3811"). Subsequently, drying by heating is performed to prepare a coating film of the adhesive composition into an adhesive layer. The thickness of the adhesive layer was 10. Mu.m. Then, the adhesive layer on the obtained release sheet was bonded to a corona-treated surface of an ethylene-methacrylic acid copolymer (EMAA) film (thickness: 80 μm, surface tension of corona-treated surface: 54 mN/m) as one surface of a base material, to obtain an adhesive sheet for invisible dicing.
Example 2
2-ethylhexyl acrylate/vinyl acetate/2-hydroxyethyl acrylate=60/20/20 (mass ratio) to give an acrylic copolymer, and the acrylic copolymer was reacted with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to 2-hydroxyethyl acrylate to give an energy ray-curable polymer (Mw: 40 ten thousand).
100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by basf corporation under the product name "Irgacure 184"), and 0.31 parts by mass of toluene diisocyanate-based crosslinking agent (manufactured by TOYO INK co., ltd., under the product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
Example 3
100 parts by mass of an acrylic copolymer (Mw: 60 ten thousand) obtained by reacting 2-ethylhexyl acrylate/methacrylate/acrylic acid=50/40/10 (mass ratio), 120 parts by mass of 5-6 functional urethane acrylate (Dainichiseika Color & Chemicals mfg. Co., ltd. Manufactured by the COMPANY "seikaeam 14-29B"), 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by the COMPANY basf, product name "Irgacure 184"), and 0.286 parts by mass of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane (mitsuishi GAS CHEMICAL compny, manufactured by inc. Manufactured by the COMPANY name "tetra d") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
Example 4
A film having a thickness of 80 μm was produced by extrusion molding of a linear low density polyethylene resin (UBE-MARUZEN POLYETHYLENE CO., LTD., product name "UMERIT 3540F") and a polypropylene resin (produced by light emitting petrochemical Co., product name "F-724 NP") using an extruder (produced by TOYO SEIKI Co., ltd.). An adhesive sheet for invisible-cut was produced in the same manner as in example 2, except that a film obtained by corona-treating one side of the film was used as a base material.
Example 5
Butyl acrylate/methyl methacrylate/2-hydroxyethyl acrylate=62/10/28 (mass ratio) to give an acrylic copolymer, and the acrylic copolymer was reacted with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to the 2-hydroxyethyl acrylate to give an energy ray-curable polymer (Mw: 40 ten thousand).
100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by basf corporation under the product name "Irgacure 184"), and 1.61 parts by mass of toluene diisocyanate-based crosslinking agent (manufactured by TOYO INK co., ltd., under the product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
Comparative example 1
An acrylic copolymer was obtained by reacting lauryl acrylate/methyl methacrylate/2-hydroxyethyl acrylate=42/30/28 (mass ratio), and an energy ray curable polymer (Mw: 40 ten thousand) was obtained by reacting the acrylic copolymer with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to 2-hydroxyethyl acrylate.
100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by basf corporation under the product name "Irgacure 184"), and 1.07 parts by mass of toluene diisocyanate-based crosslinking agent (manufactured by TOYO INK co., ltd., under the product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
Comparative example 2
2-ethylhexyl acrylate/methyl methacrylate/2-hydroxyethyl acrylate=42/30/28 (mass ratio) to give an acrylic copolymer, and the acrylic copolymer was reacted with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to the 2-hydroxyethyl acrylate to give an energy ray-curable polymer (Mw: 40 ten thousand).
100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by basf corporation under the product name "Irgacure 184"), and 1.07 parts by mass of toluene diisocyanate-based crosslinking agent (manufactured by TOYO INK co., ltd., under the product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
Comparative example 3
2-ethylhexyl acrylate/isobornyl acrylate/2-hydroxyethyl acrylate=42/30/28 (mass ratio) to give an acrylic copolymer, and the acrylic copolymer was reacted with 80 mol% of methacryloyloxyethyl isocyanate (MOI) relative to 2-hydroxyethyl acrylate to give an energy ray-curable polymer (Mw: 40 ten thousand).
100 parts by mass of the obtained energy ray-curable polymer, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by basf corporation under the product name "Irgacure 184"), and 1.07 parts by mass of toluene diisocyanate-based crosslinking agent (manufactured by TOYO INK co., ltd., under the product name "CORONATE L") as a crosslinking agent were mixed in a solvent to obtain an adhesive composition. An adhesive sheet for invisible-cut was produced in the same manner as in example 1, except that the obtained adhesive composition was used.
[ test example 1] (measurement of shear force)
A polyethylene terephthalate film (thickness: 100 μm) as a backing was bonded to the surface of the base material of the adhesive sheet for invisible dicing obtained in examples and comparative examples on the opposite side to the adhesive layer using a transient adhesive (manufactured by TOAGOSEI co., ltd., product name "Aron Alpha"), to obtain a laminate.
The laminate obtained was cut into a sheet having a length of 50mm and a width of 30mm at a temperature of 23℃and a relative humidity of 50%, and then a release sheet was peeled from the adhesive layer to obtain a sample. The sample was attached to the mirror surface of a silicon mirror wafer (thickness: 350 μm) via an adhesive layer in an environment at a temperature of 23 ℃ and a relative humidity of 50%. At this time, a load was applied to the sample back and forth 1 time by a 2kg roller, and a portion of 3mm in the longitudinal direction of the sample was attached to the silicon mirror wafer so as to be adhered thereto. Then, on the silicon mirror wafer, the sample was cut only by a cutter (cutter) so that the width of the sample became 20mm, and unnecessary samples were cutThe cut-off sheet is peeled from the substrate. As a result, as shown in FIGS. 1 and 2, a sample and a silicon mirror wafer were obtained at 20mm×3mm (60 mm) 2 ) Is attached to the test object. In fig. 1 and 2, reference numeral 1 denotes an adhesive sheet (sample) for invisible-cut with a backing, reference numeral 2 denotes a silicon mirror wafer, reference numeral 11 denotes a base material, reference numeral 12 denotes an adhesive layer, and reference numeral 13 denotes a backing.
After 20 minutes of application, a tensile test was performed under the condition of a tensile speed of 1mm/min at 23℃using an autoclave (manufactured by IMADA SEISAKUSHO CO., LTD under the product name "SDT-203NB-50R 3") to measure a shear force (N/(3 mm. Times.20 mm)). The results are shown in Table 1.
Test example 2 (determination of storage modulus of substrate)
For the substrates used in examples and comparative examples, storage modulus (MPa) at 23 ℃ was measured using the following apparatus and conditions. The results are shown in Table 1.
Measurement device: TA instruments, dynamic elastic modulus measuring device "DMA Q800"
Test initiation temperature: 0 DEG C
End of test temperature: 200 DEG C
Heating rate: 3 ℃/min
Frequency: 11Hz
Amplitude of: 20 μm
Test example 3 (determination of storage modulus of adhesive layer)
The adhesive compositions used in examples and comparative examples were applied to the release surface of the release sheet to form an adhesive layer, and the release surface of the release sheet prepared separately was pressure-bonded to the exposed adhesive layer to prepare an adhesive sheet comprising release sheet/adhesive layer/release sheet. The release sheet was peeled off from the adhesive sheet, and a plurality of adhesive layers were laminated so that the thickness became 200. Mu.m. A30 mm by 4mm rectangle (thickness: 200 μm) was punched out of the laminate of the adhesive layers obtained, and this was used as a measurement sample. For this measurement sample, the storage modulus (kPa) of the adhesive layer at 23 ℃ was measured by the following apparatus and conditions. The results are shown in Table 1.
Measurement device: TA instruments, dynamic elastic modulus measuring device "DMA Q800"
Distance between measurements: 20mm of
Test initiation temperature: -30 DEG C
End of test temperature: 120 DEG C
Heating rate: 3 ℃/min
Frequency: 11Hz
Amplitude of: 20 μm
Test example 4 (evaluation of cleaning Property)
The adhesive layers of the invisible-cut adhesive sheets obtained in examples and comparative examples were attached with a 6-inch ring frame and a mirror surface of a 6-inch silicon mirror wafer (thickness: 100 μm). Next, a modified layer was formed in the 6-inch silicon mirror wafer by irradiating a laser beam from a surface of the 6-inch silicon mirror wafer opposite to the adhesive sheet for dicing using a dicing saw (manufactured by DISCO Corporation under the product name "DFL 7360") under the following conditions. The laser irradiation was performed so that the size of the obtained chip was 8mm square.
< irradiation conditions >
Irradiation height: 68 μm from the tape side
Frequency: 90Hz
And (3) outputting: 0.3W
Processing speed: 360mm/sec
Then, the work was spread using a spreading device (product name "ME-300B" manufactured by JCM Co.) under the condition that the pull-down speed was 100mm/sec and the pull-down amount was 10mm at 23 ℃. Immediately thereafter, the chip spacing (μm) was measured using a digital microscope (manufactured by KEYENCE CORPORATION under the product name "VHX-1000"), and an average value was calculated by measuring arbitrary 5 points. The average value was defined as the chip spacing (μm) immediately after expansion. Furthermore, the cleanability was evaluated based on the following criteria based on the value of the chip interval immediately after expansion. The results are shown in Table 1.
O: the chip interval is more than 150 mu m
X: the chip spacing is less than 150 mu m
TABLE 1
As is clear from table 1, the chip interval of the invisible-cut adhesive sheet obtained in examples was sufficiently enlarged by extension, and excellent cleaning performance was exhibited.
Industrial applicability
The invisible-cutting adhesive sheet of the present invention can be suitably used in a method for manufacturing a semiconductor device, in which an expansion step and a cleaning step are performed.
Description of the reference numerals
1: adhesive sheet (sample) for invisible cutting with backing material; 11: a substrate; 12: an adhesive layer; 13: backing material; 2: silicon mirror wafer.

Claims (5)

1. An adhesive sheet for invisible dicing, which is used at least for cutting and separating a semiconductor wafer having a modified layer formed therein into individual chips in a room temperature environment, characterized in that,
comprising a base material and an adhesive layer laminated on one surface side of the base material,
the base material is a single layer, and the base material is a single layer,
when the invisible-cut adhesive sheet is attached to a silicon wafer via the adhesive layer, the shearing force at 23 ℃ of the interface between the adhesive layer and the silicon wafer is 5N/(3 mm x 20 mm) to 70N/(3 mm x 20 mm).
2. The adhesive sheet for invisible-cutting according to claim 1, wherein the adhesive layer is made of an energy ray-curable adhesive.
3. The adhesive sheet for invisible cutting according to claim 1, wherein the storage modulus of the base material at 23 ℃ is 10MPa or more and 600MPa or less.
4. A method for manufacturing a semiconductor device is characterized by comprising:
a bonding step of bonding the adhesive layer of the invisible-skin dicing adhesive sheet according to any one of claims 1 to 3 to a semiconductor wafer;
a modified layer forming step of forming a modified layer inside the semiconductor wafer;
an expanding step of expanding the invisible-cut adhesive sheet in a room temperature environment to cut and separate the semiconductor wafer having the modified layer formed therein into individual chips; and
And a cleaning step of cleaning the chips stacked on the invisible-dicing adhesive sheet in a state in which the invisible-dicing adhesive sheet is expanded.
5. The method of manufacturing a semiconductor device according to claim 4, further comprising a lamination step of laminating an adhesive film on a surface of the semiconductor wafer bonded to the invisible-dicing adhesive sheet opposite to the invisible-dicing adhesive sheet side.
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