CN111826100A - Dicing die bonding film - Google Patents

Dicing die bonding film Download PDF

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Publication number
CN111826100A
CN111826100A CN202010299872.8A CN202010299872A CN111826100A CN 111826100 A CN111826100 A CN 111826100A CN 202010299872 A CN202010299872 A CN 202010299872A CN 111826100 A CN111826100 A CN 111826100A
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Prior art keywords
adhesive layer
bonding film
pressure
sensitive adhesive
dicing
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CN202010299872.8A
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Chinese (zh)
Inventor
杉村敏正
福井章洋
大西谦司
木村雄大
高本尚英
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Nitto Denko Corp
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Nitto Denko Corp
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241Polyolefin, e.g.rubber
    • C09J7/243Ethylene or propylene polymers
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    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/29Compounds containing one or more carbon-to-nitrogen double bonds
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    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
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    • C09J133/20Homopolymers or copolymers of acrylonitrile
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    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus 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
    • H01L21/683Apparatus 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
    • H01L21/6835Apparatus 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
    • H01L21/6836Wafer tapes, e.g. grinding or dicing support tapes
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326Applications 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
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional 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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    • C09J2423/00Presence of polyolefin
    • C09J2423/04Presence of homo or copolymers of ethene
    • C09J2423/046Presence of homo or copolymers of ethene in the substrate
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    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
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    • H01L2221/683Apparatus 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
    • H01L2221/68304Apparatus 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
    • H01L2221/68327Apparatus 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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    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
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    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
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    • H01L2224/83Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319Arrangement of the layer connectors prior to mounting
    • H01L2224/83191Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
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    • H01L2224/91Methods for connecting semiconductor or solid state bodies including different methods provided for in two or more of groups H01L2224/80 - H01L2224/90
    • H01L2224/92Specific sequence of method steps
    • H01L2224/922Connecting different surfaces of the semiconductor or solid-state body with connectors of different types
    • H01L2224/9222Sequential connecting processes
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    • H01L2224/92247Sequential connecting processes the first connecting process involving a layer connector the second connecting process involving a wire connector
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    • H01L2924/15Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181Encapsulation

Abstract

Provided is a dicing die-bonding film which is less likely to float between an adhesive layer and an adhesive layer during cold expansion and normal temperature expansion, and thereafter. A dicing die-bonding film comprising: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer that is releasably adhered to the adhesive layer in the dicing tape, wherein the adhesive layer has a water contact angle of a surface on the adhesive layer adhesion side of 110 DEG or less and an arithmetic average surface roughness Ra of 1.0 [ mu ] m or less.

Description

Dicing die bonding film
Technical Field
The present invention relates to dicing die-bonding films. More specifically, the present invention relates to a dicing die-bonding film that can be used in a process of manufacturing a semiconductor device.
Background
In the manufacturing process of a semiconductor device, a dicing die bonding film is sometimes used in the process of obtaining a semiconductor chip having an adhesive film for die bonding having a size corresponding to that of the chip, that is, a semiconductor chip with an adhesive layer for die bonding. The dicing die-bonding film has a size corresponding to a semiconductor wafer to be processed, and includes, for example, a dicing tape including a base material and an adhesive layer, and a die-bonding film (adhesive layer) releasably adhering to the adhesive layer side.
As one of the methods for obtaining a semiconductor chip with an adhesive layer by dicing a die bond film, a method is known in which a step for spreading a dicing tape in the dicing die bond film to cut the die bond film is performed. The method comprises bonding a semiconductor wafer on a die bonding film obtained by cutting the die bonding film. The semiconductor wafer is processed so as to be cut together with the die-bonding film and be singulated into a plurality of semiconductor chips, for example.
Then, in order to cut the die-bonding film on the dicing tape, the dicing tape of the dicing die-bonding film is stretched in a two-dimensional direction including a radial direction and a circumferential direction of the semiconductor wafer using an expanding device. In this expanding step, the semiconductor wafer located on the die bond film is also cut at a position corresponding to the cutting position in the die bond film, and the semiconductor wafer is singulated into a plurality of semiconductor chips on the dicing die bond film or the dicing tape.
Then, the plurality of semiconductor chips with die-bonding films on the dicing tape after the dicing is subjected to the expanding step again for widening the pitch. After the cleaning step, for example, each semiconductor chip is lifted up from the lower side of the dicing tape together with the die bonding film having a size corresponding to the chip and adhering thereto by the needle member of the pickup mechanism, and picked up from the dicing tape. Thus, a semiconductor chip with a die bond film, i.e., an adhesive layer, is obtained. The semiconductor chip with the adhesive layer is fixed to an adherend such as a mounting board by die bonding via the adhesive layer.
Techniques relating to dicing die-bonding films used as described above are described in, for example, patent documents 1 to 3 below.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-2173
Patent document 2: japanese patent application laid-open No. 2010-177401
Patent document 3: japanese patent laid-open publication No. 2016-115804
Disclosure of Invention
Problems to be solved by the invention
In recent years, due to the demand for higher capacity of semiconductors, circuit layers have been made multilayered and silicon layers have been made thinner. However, the circuit layer is multilayered, the thickness (total thickness) of the circuit layer increases, and the proportion of the resin contained in the circuit layer tends to increase, and thus the difference in linear expansion rate between the multilayered circuit layer and the silicon layer that is thinned becomes significant, and the semiconductor chip is likely to warp. Therefore, when a conventional dicing die-bonding film is used, particularly in a semiconductor chip in which a circuit layer with a die-bonding film obtained after dicing is multilayered, the following problems arise: peeling (floating) is likely to occur at the interface between the pressure-sensitive adhesive layer of the dicing tape and the die-bonding film in and after the expansion step (cold expansion and room-temperature expansion described later) (for example, in the cleaning step, during the period until the pickup). If the floating occurs, the semiconductor chip is likely to slip off after the expanding step (during the cleaning step, the treatment step, and the like).
The present invention has been made in view of the above problems, and an object thereof is to provide a dicing die-bonding film in which floating is less likely to occur between an adhesive layer and an adhesive layer during cold expansion and normal temperature expansion, and thereafter.
Means for solving the problems
As a result of intensive studies to achieve the above object, the present inventors have found that, when a dicing die-bonding film including: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer releasably adhered to the adhesive layer in the dicing tape, wherein the adhesive layer has a water contact angle of 110 DEG or less on a surface on a side to which the adhesive layer is adhered, and an arithmetic average surface roughness Ra of 1.0 [ mu ] m or less. The present invention has been completed based on the above findings.
That is, the present invention provides a dicing die-bonding film including: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer releasably adhered to the adhesive layer in the dicing tape, wherein the adhesive layer has a water contact angle of 110 DEG or less on a surface on a side to which the adhesive layer is adhered, and an arithmetic average surface roughness Ra of 1.0 [ mu ] m or less.
The dicing die-bonding film of the present invention includes a dicing tape and an adhesive layer. The dicing tape has a laminated structure including a substrate and an adhesive layer. The adhesive layer is releasably adhered to the adhesive layer in the dicing tape. The dicing die-bonding film of such a configuration can be used to obtain a semiconductor chip with an adhesive layer in the manufacturing process of a semiconductor device.
In the manufacturing process of the semiconductor device, as described above, in order to obtain the semiconductor chip with the adhesive layer, a spreading step using a dicing die bonding film, that is, a spreading step for cleaving, may be performed. In this spreading step, it is necessary to appropriately apply a cutting force to the adhesive layer on the dicing tape in the dicing die-bonding film. The dicing tape pressure-sensitive adhesive layer in the dicing die-bonding film of the present invention has a water contact angle of the surface on the adhesive layer adhesion side of 110 DEG or less and an arithmetic average surface roughness Ra of 1.0 [ mu ] m or less. The dicing die-bonding film of the present invention having such a configuration has suitably excellent adhesion between the pressure-sensitive adhesive layer and the adhesive layer, and can suppress the occurrence of peeling (floating) between the pressure-sensitive adhesive layer and the adhesive layer after the spreading step.
In the dicing die-bonding film of the present invention, it is preferable that the surface of the pressure-sensitive adhesive layer (the surface on the side to which the pressure-sensitive adhesive layer is in contact) has a polar component value of surface free energy, which is obtained from Kaelble Uy equation using the contact angle of water and the contact angle of diiodomethane, of 0.10 or more. With the dicing die-bonding film of the present invention having such a configuration, the difference in polar components between the dicing die-bonding film and the surface of the adhesive layer is reduced, and the affinity between the surface of the adhesive layer and the surface of the adhesive layer is improved, so that the adhesiveness between the adhesive layer and the adhesive layer becomes more appropriate, and the occurrence of peeling (floating) between the adhesive layer and the adhesive layer in the expanding step and thereafter can be further suppressed.
In the dicing die-bonding film of the present invention, the pressure-sensitive adhesive layer preferably contains an acrylic polymer containing a hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group and a hydroxyl group-containing monomer as monomer components. The dicing die-bonding film of the present invention having such a structure can easily design an adhesive layer having a surface with a water contact angle of 110 ° or less and an arithmetic average surface roughness Ra of 1.0 μm or less.
The adhesive layer preferably contains a polyisocyanate compound as a crosslinking agent. With the dicing die-bonding film of the present invention having such a configuration, it is possible to easily design a pressure-sensitive adhesive layer having a surface with a water contact angle of 110 ° or less and an arithmetic average surface roughness Ra of 1.0 μm or less, and it is possible to easily design a radiation-curable pressure-sensitive adhesive layer capable of distinguishing between a state in which the pressure-sensitive adhesive layer exhibits a relatively high adhesive force and a state in which the pressure-sensitive adhesive layer exhibits a relatively low adhesive force.
Invention of the inventionEffect of (1)
The dicing die-bonding film of the present invention is less likely to float between the adhesive layer and the pressure-sensitive adhesive layer after the spreading step using the dicing die-bonding film for obtaining the semiconductor chip with the adhesive layer. In particular, even when a semiconductor chip in which circuit layers are multilayered is used, floating is less likely to occur.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of the dicing die-bonding film of the present invention.
Fig. 2 shows a part of the steps in the method for manufacturing a semiconductor device using the dicing die-bonding film shown in fig. 1.
Fig. 3 shows a subsequent process to that shown in fig. 2.
Fig. 4 shows a subsequent process to that shown in fig. 3.
Fig. 5 shows a subsequent process to that shown in fig. 4.
Fig. 6 shows a subsequent process to that shown in fig. 5.
Fig. 7 shows a subsequent process to that shown in fig. 6.
Fig. 8 shows a part of the steps in a modification of the method for manufacturing a semiconductor device using the dicing die-bonding film shown in fig. 1.
Fig. 9 shows a part of the steps in a modification of the method for manufacturing a semiconductor device using the dicing die-bonding film shown in fig. 1.
Fig. 10 shows a part of the steps in a modification of the method for manufacturing a semiconductor device using the dicing die-bonding film shown in fig. 1.
Fig. 11 shows a part of the steps in a modification of the method for manufacturing a semiconductor device using the dicing die-bonding film shown in fig. 1.
Description of the reference numerals
1 dicing die-bonding film
10 cutting belt
11 base material
12 adhesive layer
20. 21 adhesive layer
W, 30A, 30C semiconductor wafer
30B semiconductor wafer division body
30a dividing groove
30b modified region
31 semiconductor chip
Detailed Description
[ dicing die-bonding film ]
The dicing die-bonding film of the present invention comprises: a dicing tape having a laminated structure including a substrate and an adhesive layer; and an adhesive layer that is releasably bonded to the adhesive layer in the dicing tape. An embodiment of the dicing die-bonding film of the present invention will be described below.
Fig. 1 is a schematic cross-sectional view showing one embodiment of the dicing die-bonding film of the present invention. As shown in fig. 1, the dicing die-bonding film 1 includes: cutting the tape 10; and an adhesive layer 20 laminated on the adhesive layer 12 in the dicing tape 10, and can be used in a spreading step in a process of obtaining a semiconductor chip with an adhesive layer in the manufacture of a semiconductor device.
The dicing die-bonding film 1 has a disk shape, and its size corresponds to a semiconductor wafer which is a processing object in the manufacturing process of a semiconductor device. The dicing die-bonding film 1 has a diameter in a range of, for example, 345 to 380mm (12-inch wafer-compatible type), 245 to 280mm (8-inch wafer-compatible type), 195 to 230mm (6-inch wafer-compatible type), or 495 to 530mm (18-inch wafer-compatible type).
The dicing tape 10 in the dicing die-bonding film 1 has a laminated structure including a base material 11 and an adhesive layer 12. The dicing die-bonding film 1 has a water contact angle of 110 DEG or less and an arithmetic mean surface roughness Ra of 1.0 [ mu ] m or less on the surface 12a of the pressure-sensitive adhesive layer 12 on the side to which the adhesive layer 20 adheres.
(substrate)
The base material in the dicing tape is an element that functions as a support in the dicing tape or the dicing die-bonding film. Examples of the substrate include a plastic substrate (particularly, a plastic film). The substrate may be a single layer or a laminate of substrates of the same or different types.
Examples of the resin constituting the plastic substrate include: polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homo-polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer; a polyurethane; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); a polycarbonate; a polyimide; polyether ether ketone; a polyetherimide; polyamides such as aromatic polyamides and wholly aromatic polyamides; polyphenylene sulfide; a fluororesin; polyvinyl chloride; polyvinylidene chloride; a cellulose resin; silicone resins, and the like. The base material preferably contains an ethylene-vinyl acetate copolymer as a main component from the viewpoint of ensuring good heat shrinkability of the base material and easily maintaining the chip pitch distance by partial heat shrinkage of a dicing tape or the base material in a normal temperature expanding step described later.
The main component of the base material is a component occupying the largest mass ratio among the constituent components. The resin may be used alone or in combination of two or more. When the pressure-sensitive adhesive layer is a radiation-curable pressure-sensitive adhesive layer as described later, the substrate preferably has radiation permeability.
When the substrate is a plastic film, the plastic film may be unoriented or oriented in at least one direction (one-axis direction, two-axis direction, etc.). The plastic film is capable of heat shrinking in at least one direction when oriented in the at least one direction. When the dicing tape has heat shrinkability, the outer peripheral portion of the semiconductor wafer of the dicing tape can be heat shrunk, whereby the semiconductor chips with the adhesive layer after singulation can be fixed in a state where the interval between the semiconductor chips is widened, and therefore the semiconductor chips can be easily picked up. In order to impart isotropic heat shrinkability to the substrate and the dicing tape, it is preferable that the substrate is a biaxially oriented film. The plastic film oriented in at least one direction may be obtained by stretching an unstretched plastic film in at least one direction (uniaxial stretching, biaxial stretching, or the like).
The heat shrinkage rate of the base material and the dicing tape in a heat treatment test performed under the conditions of a heating temperature of 100 ℃ and a heating time of 60 seconds is preferably 1 to 30%, more preferably 2 to 25%, even more preferably 3 to 20%, and particularly preferably 5 to 20%. The heat shrinkage ratio is preferably a heat shrinkage ratio in at least one of the MD direction and the TD direction.
For the purpose of improving the adhesiveness to the pressure-sensitive adhesive layer, the holding property, and the like, the pressure-sensitive adhesive layer-side surface of the substrate may be subjected to physical treatments such as corona discharge treatment, plasma treatment, sanding treatment, ozone exposure treatment, flame exposure treatment, high-voltage shock exposure treatment, and ionizing radiation treatment; chemical treatments such as chromic acid treatment; surface treatment such as easy adhesion treatment with a coating agent (primer). In addition, in order to impart antistatic ability, a conductive vapor deposition layer containing a metal, an alloy, an oxide thereof, or the like may be provided on the surface of the base material. The entire surface of the substrate on the pressure-sensitive adhesive layer side is preferably subjected to a surface treatment for improving adhesion.
From the viewpoint of ensuring the strength with which the base material functions as a support for the dicing tape and the dicing die-bonding film, the thickness of the base material is preferably 40 μm or more, more preferably 50 μm or more, still more preferably 55 μm or more, and particularly preferably 60 μm or more. From the viewpoint of achieving appropriate flexibility of the dicing tape and the dicing die-bonding film, the thickness of the base material is preferably 200 μm or less, more preferably 180 μm or less, and still more preferably 150 μm or less.
(adhesive layer)
In the pressure-sensitive adhesive layer of the dicing die-bonding film of the present invention, as described above, the water contact angle of the surface on the adhesive layer adhesion side is 110 ° or less, and the arithmetic average surface roughness Ra is 1.0 μm or less. With such a configuration, the dicing die-bonding film of the present invention has an appropriately excellent adhesion between the pressure-sensitive adhesive layer and the adhesive layer, and can suppress the occurrence of peeling (floating) between the pressure-sensitive adhesive layer and the adhesive layer after the spreading step.
The surface (surface 12a) of the pressure-sensitive adhesive layer on the side to which the pressure-sensitive adhesive layer is in contact has an arithmetic average surface roughness (Ra) of 1.0 μm or less, preferably 0.5 μm or less, and more preferably 0.3 μm or less. The Ra can be obtained by measuring the surface of the pressure-sensitive adhesive layer in the portion of the dicing die-bonding film of the present invention where the pressure-sensitive adhesive layer is not laminated. The arithmetic average surface roughness can be measured according to JIS B0601.
The water contact angle of the surface (surface 12a) of the pressure-sensitive adhesive layer on the adhesive layer adhesion side is 110 ° or less, preferably 108 ° or less, and more preferably 105 ° or less. The water contact angle can be obtained by measuring the surface of the pressure-sensitive adhesive layer in the portion of the dicing die-bonding film of the present invention where the pressure-sensitive adhesive layer is not laminated.
The water contact angle is, for example, 80 ° or more, preferably 84 ° or more, and more preferably 88 ° or more. When the water contact is 80 ° or more, the fusion bonding between the pressure-sensitive adhesive layer and the adhesive layer can be suppressed, and the pressure-sensitive adhesive layer and the adhesive layer are less likely to be peeled off when they are intentionally peeled off.
The value of the polar component of the surface free energy obtained from the Kaelble Uy formula of the contact angle of water and the contact angle of diiodomethane used on the surface (surface 12a) of the pressure-sensitive adhesive layer on the adhesive layer adhesion side is preferably 0.10 or more, more preferably 0.20 or more, and still more preferably 0.40 or more. When the value of the polar component is 0.10 or more, the difference in the polar component from the surface of the adhesive layer is small, and the affinity between the surface of the adhesive layer and the surface of the adhesive layer is improved, so that the adhesiveness between the adhesive layer and the adhesive layer becomes more appropriate, and the occurrence of peeling (floating) between the adhesive layer and the adhesive layer in the spreading step and thereafter can be further suppressed. The value of the polar component is γ s in the following formula (1) used for determining the surface free energypThe following equation (2) and the following equation (3) can be used for the calculation.
γs=γsd+γsp(1)
γw(1+cosθw)=2(γsdγwd)1/2+2(γspγwp)1/2(2)
γi(1+cosθi)=2(γsdγid)1/2+2(γspγip)1/2(3)
In the above formulae (1) to (3), γ s represents the surface free energy of the pressure-sensitive adhesive layer, and γ sdA dispersing component, γ s, representing the surface free energy of the adhesive layerpA polar component representing the surface free energy of the adhesive layer, and γ w represents 72.8mJ/m2,γwdRepresents 21.8mJ/m2,γwpRepresents 51.0mJ/m2γ i represents 50.8mJ/m2,γidRepresents 48.5mJ/m2,γipRepresents 2.3mJ/m2θ w represents a water contact angle of the surface of the adhesive layer, and θ i represents a diiodomethane contact angle of the surface of the adhesive layer. Gamma w, gamma wd、γwp、γi、γidAnd γ ipAre known literature values.
The pressure-sensitive adhesive layer of the dicing tape is preferably a pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) containing an acrylic polymer as a base polymer. The acrylic polymer is a polymer containing a constituent unit derived from an acrylic monomer (a monomer component having a (meth) acryloyl group in a molecule) as a constituent unit of the polymer.
The acrylic polymer is preferably a polymer having the largest content of constituent units derived from (meth) acrylate in terms of mass ratio. The acrylic polymer may be used alone or in combination of two or more. In the present specification, "(meth) acrylic acid" means "acrylic acid" and/or "methacrylic acid" ("either or both of acrylic acid" and "methacrylic acid"), and the like.
Examples of the (meth) acrylate include a hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group. Examples of the hydrocarbon group-containing (meth) acrylate include alkyl (meth) acrylates, cycloalkyl (meth) acrylates, and aryl (meth) acrylates.
Examples of the alkyl (meth) acrylate include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, isodecyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl (meth) acrylates and the like.
Examples of the cycloalkyl (meth) acrylate include: cyclopentyl esters, cyclohexyl esters of (meth) acrylic acid, and the like. Examples of the aryl (meth) acrylate include: phenyl and benzyl (meth) acrylates.
Examples of the hydrocarbyl (meth) acrylate having an alkoxy group include those obtained by substituting 1 or more hydrogen atoms in the hydrocarbyl group in the above-mentioned hydrocarbyl (meth) acrylate with an alkoxy group, and examples thereof include 2-methoxymethyl ester, 2-methoxyethyl ester, and 2-methoxybutyl ester of (meth) acrylic acid.
The hydrocarbon-containing (meth) acrylate optionally having an alkoxy group may be used alone or in combination of two or more.
In one embodiment, the total number of carbon atoms in the ester portion (including the total number of carbon atoms in the alkoxy group when the alkyl group is present) is preferably 6 to 10. Particularly preferred is a hydrocarbon group-containing (meth) acrylate in which the total number of carbon atoms in the hydrocarbon group is 6 to 10. In this case, the spreading step and the subsequent suppression of floating between the adhesive layer and the good pickup property in the pickup step can be more easily achieved at the same time.
In another embodiment, the total number of carbon atoms in the ester portion (including the total number of carbon atoms in the alkoxy group in the case of having an alkoxy group) is preferably 2 to 4 in the above-mentioned hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group. Particularly preferred is a hydrocarbon group-containing (meth) acrylate in which the total number of carbon atoms in the hydrocarbon group is 2 to 4. In this case, since the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group has a relatively high polarity, even if the proportion of the polar group-containing monomer is relatively small, the water contact angle of the surface of the pressure-sensitive adhesive layer can be easily made 110 ° or less.
In order to appropriately exhibit basic characteristics such as adhesiveness based on the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in the pressure-sensitive adhesive layer, the proportion of the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in all monomer components for forming the acrylic polymer is preferably 20 mol% or more, and more preferably 30 mol% or more. More preferably 40 mol% or more.
In the present specification, the monomer component does not include a compound having a radiation-polymerizable group (for example, a compound having a 2 nd functional group and a radiation-polymerizable carbon-carbon double bond described later) in a stage of incorporating the polymer before the pressure-sensitive adhesive layer is irradiated with radiation.
The acrylic polymer may contain a constituent unit derived from another monomer component copolymerizable with the above hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group for the purpose of modification of cohesive force, heat resistance, and the like. Examples of the other monomer components include polar group-containing monomers such as carboxyl group-containing monomers, anhydride-containing monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and nitrogen atom-containing monomers.
Examples of the carboxyl group-containing monomer include: acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like.
Examples of the acid anhydride monomer include: maleic anhydride, itaconic anhydride, and the like. Examples of the hydroxyl group-containing monomer include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
Examples of the glycidyl group-containing monomer include: glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and the like.
Examples of the sulfonic acid group-containing monomer include: styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid, and the like.
Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate and the like.
Examples of the nitrogen atom-containing monomer include a morpholine-containing monomer such as (meth) acryloylmorpholine, a cyano-containing monomer such as (meth) acrylonitrile, and an amide-containing monomer such as (meth) acrylamide.
Among the other monomer components, preferred are hydroxyl group-containing monomers and nitrogen atom-containing monomers (particularly morpholine group-containing monomers), and more preferred are 2-hydroxyethyl (meth) acrylate (2-hydroxyethyl (meth) acrylate) and (meth) acryloylmorpholine. That is, the acrylic polymer preferably contains a constituent unit derived from 2-hydroxyethyl (meth) acrylate and/or a constituent unit derived from (meth) acryloylmorpholine.
The other monomer component may be used alone or in combination of two or more.
In order to appropriately exhibit basic characteristics such as adhesiveness based on the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in the pressure-sensitive adhesive layer, the total proportion of the polar group-containing monomers in all the monomer components for forming the acrylic polymer is preferably 60 mol% or less, and more preferably 50 mol% or less. In addition, the total proportion of the polar group-containing monomers is preferably 10 mol% or more, and more preferably 15 mol% or more, from the viewpoint of easily designing the water contact angle of the surface of the pressure-sensitive adhesive layer to 110 ° or less.
In order to appropriately exhibit basic characteristics such as adhesiveness based on the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in the pressure-sensitive adhesive layer, the proportion of the constituent unit derived from the hydroxyl group-containing monomer in the entire monomer components for forming the acrylic polymer is preferably 5 mol% or more, and more preferably 10 mol% or more. The above ratio is, for example, 80 mol% or less, and may be 70 mol% or less and 60 mol% or less.
In the case where the above-mentioned nitrogen atom-containing monomer is used as the monomer component for forming the acrylic polymer, the proportion of the constituent unit derived from the nitrogen atom-containing monomer in the entire monomer components for forming the acrylic polymer is preferably 3 mol% or more, and more preferably 5 mol% or more, from the viewpoint that the water contact angle of the surface of the pressure-sensitive adhesive layer can be easily designed to be 110 ° or less. The above ratio is, for example, 50 mol% or less, and may be 30 mol% or less and 20 mol% or less.
The acrylic polymer may contain a constituent unit derived from a polyfunctional monomer copolymerizable with a monomer component forming the acrylic polymer, in order to form a crosslinked structure in the polymer skeleton. Examples of the polyfunctional monomer include: examples of the monomer include monomers having a (meth) acryloyl group and another reactive functional group in the molecule, such as hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate (for example, polyglycidyl (meth) acrylate), polyester (meth) acrylate, and urethane (meth) acrylate.
The polyfunctional monomer may be used alone or in combination of two or more. In order to appropriately exhibit basic characteristics such as adhesiveness based on the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in the pressure-sensitive adhesive layer, the ratio of the polyfunctional monomer in the total monomer components for forming the acrylic polymer is preferably 40 mol% or less, and more preferably 30 mol% or less.
The acrylic polymer preferably contains a structural unit derived from a monomer having a 1 st functional group (for example, the polar group-containing monomer), and also contains a structural unit derived from a compound having a 2 nd functional group reactive with the 1 st functional group and a radiation-polymerizable functional group. When the acrylic polymer has such a structure, the radiation-curable pressure-sensitive adhesive described later can be easily designed.
Examples of the combination of the 1 st functional group and the 2 nd functional group include: carboxyl and epoxy, epoxy and carboxyl, carboxyl and aziridine, aziridine and carboxyl, hydroxyl and isocyanate, isocyanate and hydroxyl, and the like. Among these, from the viewpoint of following the easiness of the reaction, a combination of a hydroxyl group and an isocyanate group, and a combination of an isocyanate group and a hydroxyl group are preferable. Among them, a polymer having an isocyanate group with high reactivity is difficult to prepare, and from the viewpoint of the preparation and ease of handling of an acrylic polymer having a hydroxyl group, a combination in which the 1 st functional group is a hydroxyl group and the 2 nd functional group is an isocyanate group is preferable.
The acrylic polymer particularly preferably contains a structural unit derived from a hydroxyl group-containing monomer and a structural unit derived from a compound having a radiation-polymerizable carbon-carbon double bond (particularly a (meth) acryloyl group) and an isocyanate group.
Examples of the compounds having a radiation-polymerizable carbon-carbon double bond and an isocyanate group include methacryloyl isocyanate, 2-acryloxyethyl isocyanate, 2-methacryloxyethyl isocyanate, and m-isopropenyl- α, α -dimethylbenzyl isocyanate. Among them, 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate are preferable. Examples of the acrylic polymer having a hydroxyl group include acrylic polymers containing constituent units derived from the above-mentioned hydroxyl group-containing monomer, and ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.
The molar ratio [ former/latter ] of the constituent unit derived from the monomer having the 1 st functional group to the compound having the 2 nd functional group and the radiation-polymerizable functional group is preferably 0.95 or more, more preferably 1.00 or more, further preferably 1.05 or more, and particularly preferably 1.10 or more. When the molar ratio is 0.95 or more, the bonding between the 1 st functional group (for example, hydroxyl group) and the 2 nd functional group (for example, isocyanate group) can be sufficiently promoted, but it is estimated that the unreacted 1 st functional group in the acrylic polymer in the pressure-sensitive adhesive layer remains to some extent, the peeling force between the pressure-sensitive adhesive layer and the substrate is further increased, and the pressure-sensitive adhesive layer is less likely to be broken during expansion. The above molar ratio is, for example, 10.00 or less, and may be 5.00 or less, 3.00 or less, 2.00 or less, 1.50 or less, or 1.30 or less.
In particular, the molar ratio of the hydroxyl group-containing monomer to 2-methacryloyloxyethyl isocyanate [ hydroxyl group-containing monomer/2-methacryloyloxyethyl isocyanate ] is preferably within the above range.
The acrylic polymer can be obtained by polymerizing one or more monomer components including an acrylic monomer. Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.
The adhesive layer or the adhesive forming the adhesive layer may contain a crosslinking agent. For example, when an acrylic polymer is used as the base polymer, the acrylic polymer can be crosslinked to further reduce low molecular weight substances in the adhesive layer. In addition, the number average molecular weight of the acrylic polymer can be increased.
Examples of the crosslinking agent include: polyisocyanate compounds, epoxy compounds, polyol compounds (such as polyphenol compounds), aziridine compounds, melamine compounds, and the like. Among them, polyisocyanate compounds are preferable. In this case, it is possible to easily design a pressure-sensitive adhesive layer having a surface with a water contact angle of 110 ° or less and an arithmetic average surface roughness Ra of 1.0 μm or less, and it is possible to easily design a radiation-curable pressure-sensitive adhesive layer capable of distinguishing between a state in which a relatively high adhesive force is exhibited and a state in which a relatively low adhesive force is exhibited by using the pressure-sensitive adhesive layer. When the crosslinking agent is used, the amount thereof is preferably about 5 parts by mass or less, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the base polymer.
The mass average molecular weight of the acrylic polymer (after crosslinking when a crosslinking agent is used) is preferably 30 ten thousand or more (for example, 30 to 140 ten thousand), and more preferably 35 ten thousand or more. When the mass average molecular weight is 30 ten thousand or more, the amount of low molecular weight substances in the pressure-sensitive adhesive layer tends to be small, and contamination of the pressure-sensitive adhesive layer, the semiconductor wafer, and the like can be further suppressed.
The pressure-sensitive adhesive layer may be a pressure-sensitive adhesive layer whose adhesive force can be intentionally reduced by an external action during the use of the dicing die-bonding film (adhesive force-reducible pressure-sensitive adhesive layer), or a pressure-sensitive adhesive layer whose adhesive force is hardly or not reduced by an external action during the use of the dicing die-bonding film (adhesive force-nondecreasing pressure-sensitive adhesive layer), and may be appropriately selected depending on a method, conditions, and the like for singulating a semiconductor wafer into pieces using the dicing die-bonding film.
In the case where the adhesive layer is a pressure-sensitive adhesive layer of a type having a reduced adhesive force, a state in which the adhesive layer exhibits a relatively high adhesive force and a state in which the adhesive layer exhibits a relatively low adhesive force can be distinguished from each other in the manufacturing process and the using process of the dicing die-bonding film. For example, in the production process of the dicing die-bonding film, when the adhesive layer is bonded to the adhesive layer of the dicing tape, the adherend such as the adhesive layer can be inhibited and prevented from floating from the adhesive layer by the state of relatively high adhesive force exhibited by the adhesive layer when the dicing die-bonding film is used in the dicing step, and on the other hand, in the subsequent pick-up step for picking up the semiconductor chip with the adhesive layer from the dicing tape of the dicing die-bonding film, pick-up can be easily performed by reducing the adhesive force of the adhesive layer.
Examples of the pressure-sensitive adhesive for forming such a pressure-sensitive adhesive layer having a reduced adhesive strength include a radiation-curable pressure-sensitive adhesive and a heat-expandable pressure-sensitive adhesive. As the adhesive for forming the adhesive layer having a reduced adhesive strength, only one adhesive may be used, or two or more adhesives may be used.
As the radiation-curable adhesive, for example, an adhesive of a type that is cured by irradiation with electron beams, ultraviolet rays, α rays, β rays, γ rays, or X rays can be used, and an adhesive of a type that is cured by irradiation with ultraviolet rays (an ultraviolet-curable adhesive) is particularly preferably used.
Examples of the radiation curable adhesive include an additive type radiation curable adhesive containing: a base polymer such as the above-mentioned acrylic polymer, and a radiation-polymerizable monomer component or oligomer component having a functional group such as a radiation-polymerizable carbon-carbon double bond.
Examples of the radiation-polymerizable monomer component include: urethane (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and the like.
Examples of the radiation-polymerizable oligomer component include various oligomers such as urethane type, polyether type, polyester type, polycarbonate type, and polybutadiene type, and the molecular weight is preferably about 100 to 30000.
The content of the radiation-curable monomer component and oligomer component in the radiation-curable pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is, for example, 5 to 500 parts by mass, preferably about 40 to 150 parts by mass, based on 100 parts by mass of the base polymer.
As the additive type radiation-curable pressure-sensitive adhesive, for example, one disclosed in Japanese patent application laid-open No. 60-196956 can be used.
The radiation-curable pressure-sensitive adhesive may be an internal type radiation-curable pressure-sensitive adhesive containing a base polymer having a functional group such as a radiation-polymerizable carbon-carbon double bond at a polymer side chain, a polymer main chain, or a polymer main chain end. When such an internal radiation curable pressure-sensitive adhesive is used, it tends to be possible to suppress an undesirable change in adhesive properties with time due to the movement of low-molecular-weight components in the pressure-sensitive adhesive layer to be formed.
As the base polymer contained in the internal radiation curable pressure-sensitive adhesive, an acrylic polymer is preferable. Examples of the method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer include the following methods: after the acrylic polymer is obtained by polymerizing (copolymerizing) the raw material monomer containing the monomer component having the 1 st functional group, the compound having the 2 nd functional group and a radiation-polymerizable carbon-carbon double bond is subjected to a condensation reaction or an addition reaction with the acrylic polymer while maintaining the radiation-polymerizability of the carbon-carbon double bond.
The radiation curable adhesive preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include: alpha-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphorquinone, halogenated ketones, acyl phosphine oxides, acyl phosphonate esters, and the like.
Examples of the α -ketols include: 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α -hydroxy- α, α' -dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, and the like.
Examples of the acetophenone compounds include: methoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl ] -2-morpholinopropan-1-one and the like.
Examples of the benzoin ether compound include: benzoin ethyl ether, benzoin isopropyl ether, anisoin methyl ether, and the like. Examples of the ketal compounds include: benzil dimethyl ketal, and the like.
Examples of the aromatic sulfonyl chloride-based compound include: 2-naphthalenesulfonyl chloride, and the like. Examples of the photoactive oxime compounds include: 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like.
Examples of the benzophenone compound include: benzophenone, benzoylbenzoic acid, 3' -dimethyl-4-methoxybenzophenone and the like.
Examples of the thioxanthone compound include: thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4-dimethylthioxanthone, isopropylthioxanthone, 2, 4-dichlorothioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and the like.
The content of the photopolymerization initiator in the radiation-curable adhesive is, for example, 0.05 to 20 parts by mass per 100 parts by mass of the base polymer.
The heat-expandable adhesive is an adhesive containing a component (a foaming agent, heat-expandable microspheres, or the like) which expands and expands by heating.
Examples of the blowing agent include various inorganic blowing agents and organic blowing agents. Examples of the inorganic foaming agent include: ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, azides, and the like. Examples of the organic foaming agent include: chlorofluoroalkanes such as trichlorofluoromethane and dichlorofluoromethane; azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate; hydrazine compounds such as p-toluenesulfonyl hydrazide, diphenylsulfone-3, 3 '-disulfonyl hydrazide, 4' -oxybis-benzenesulfonyl hydrazide and allyldisulfonyl hydrazide; semicarbazide compounds such as p-toluenesulfonyl semicarbazide and 4, 4' -oxybis (benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholinyl-1, 2,3, 4-thiatriazole; and N-nitroso compounds such as N, N ' -dinitrosopentamethylenetetramine and N, N ' -dimethyl-N, N ' -dinitrosoterephthalamide.
Examples of the thermally expandable microspheres include microspheres in which a substance that is easily vaporized and expanded by heating is contained in a shell. Examples of the substance which is easily vaporized and expanded by heating include: isobutane, propane, pentane, etc. The heat-expandable microspheres can be produced by encapsulating a substance that is easily vaporized and expanded by heating in a shell-forming substance by an agglomeration method, an interfacial polymerization method, or the like. As the shell-forming substance, a substance exhibiting thermal fusion properties or a substance which can be broken by the thermal expansion effect of the encapsulated substance can be used. Examples of such substances include: vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, polysulfone, and the like.
Examples of the non-reduced adhesive force pressure-sensitive adhesive layer include pressure-sensitive adhesive layers. The pressure-sensitive adhesive layer includes an adhesive layer having the following configuration: the pressure-sensitive adhesive layer formed of the radiation-curable pressure-sensitive adhesive described in the adhesion-reducing pressure-sensitive adhesive layer is cured by irradiation with radiation in advance and still has a certain adhesion. As the adhesive for forming the non-adhesive-force-reducing adhesive layer, one kind of adhesive may be used, or two or more kinds of adhesives may be used.
The entire pressure-sensitive adhesive layer may be a non-adhesive-force-reducing pressure-sensitive adhesive layer, or a part of the pressure-sensitive adhesive layer may be a non-adhesive-force-reducing pressure-sensitive adhesive layer. For example, when the pressure-sensitive adhesive layer has a single-layer structure, the pressure-sensitive adhesive layer may be a non-adhesive-force-reducing pressure-sensitive adhesive layer as a whole, or a pressure-sensitive adhesive layer may be a non-adhesive-force-reducing pressure-sensitive adhesive layer at a predetermined portion (for example, an area located outside a central area as an attachment target area of the ring frame) and a pressure-sensitive adhesive-force-reducing pressure-sensitive adhesive layer at another portion (for example, a central area as an attachment target area of the semiconductor wafer).
When the pressure-sensitive adhesive layer has a laminated structure, all of the pressure-sensitive adhesive layers in the laminated structure may be pressure-sensitive adhesive layers having a non-reduced adhesive strength, or some of the pressure-sensitive adhesive layers in the laminated structure may be pressure-sensitive adhesive layers having a non-reduced adhesive strength.
The pressure-sensitive adhesive layer (radiation-curable pressure-sensitive adhesive layer after radiation irradiation) in a form in which the pressure-sensitive adhesive layer formed of a radiation-curable pressure-sensitive adhesive (radiation-non-irradiation radiation-curable pressure-sensitive adhesive layer) is cured in advance by irradiation with radiation has a reduced adhesive force by irradiation with radiation, but exhibits adhesiveness due to the contained polymer component, and can allow the pressure-sensitive adhesive layer of the dicing tape to exhibit the lowest adhesive force in the dicing step or the like.
In the case of using a radiation-curable pressure-sensitive adhesive layer that has been irradiated with radiation, the entire pressure-sensitive adhesive layer may be a radiation-curable pressure-sensitive adhesive layer that has been irradiated with radiation in the plane expansion direction of the pressure-sensitive adhesive layer, or a part of the pressure-sensitive adhesive layer may be a radiation-curable pressure-sensitive adhesive layer that has been irradiated with radiation and the other part may be a radiation-curable pressure-sensitive adhesive layer that has not been irradiated with radiation.
In the present specification, the "radiation-curable pressure-sensitive adhesive layer" refers to a pressure-sensitive adhesive layer formed from a radiation-curable pressure-sensitive adhesive, and includes both a radiation-non-radiation-curable pressure-sensitive adhesive layer having radiation-curability and a radiation-cured pressure-sensitive adhesive layer in which the pressure-sensitive adhesive layer is cured by radiation irradiation.
As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, a known or conventional pressure-sensitive adhesive can be used, and an acrylic adhesive or a rubber adhesive containing an acrylic polymer as a base polymer can be preferably used. When the adhesive layer contains an acrylic polymer as the pressure-sensitive adhesive, the acrylic polymer is preferably a polymer containing a constituent unit derived from a (meth) acrylate ester as a constituent unit in the largest proportion by mass. As the acrylic polymer, for example, the acrylic polymer described as the acrylic polymer that can be contained in the pressure-sensitive adhesive layer can be used.
The pressure-sensitive adhesive layer or the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer may contain, in addition to the above components, known or conventional additives used in the pressure-sensitive adhesive layer, such as a crosslinking accelerator, a tackifier, an antioxidant, and a colorant (a pigment, a dye, etc.).
Examples of the colorant include compounds that are colored by irradiation with radiation. When a compound which is colored by irradiation with radiation is contained, only the portion irradiated with radiation can be colored. The compound which is colored by irradiation with radiation is colorless or pale before irradiation with radiation, and is colored by irradiation with radiation, and examples thereof include leuco dyes and the like. The amount of the compound which is colored by irradiation with radiation is not particularly limited and can be selected as appropriate.
The thickness of the pressure-sensitive adhesive layer is not particularly limited, and when the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed of a radiation-curable pressure-sensitive adhesive, from the viewpoint of achieving a balance in the adhesive strength of the pressure-sensitive adhesive layer to the pressure-sensitive adhesive layer before and after radiation curing, the thickness is preferably about 1 to 50 μm, more preferably 2 to 30 μm, and still more preferably 5 to 25 μm.
(adhesive layer)
The adhesive layer has a function as an adhesive exhibiting thermosetting property for die bonding, and further has a function of adhesion for holding a workpiece such as a semiconductor wafer and a frame member such as a ring frame, if necessary. The adhesive layer can be cut by applying a tensile stress, and the adhesive layer can be used by cutting the adhesive layer by applying a tensile stress.
The adhesive layer and the adhesive constituting the adhesive layer may contain a thermosetting resin and, for example, a thermoplastic resin as an adhesive component, or may contain a thermoplastic resin having a thermosetting functional group capable of reacting with a curing agent to bond. When the adhesive constituting the adhesive layer contains a thermoplastic resin having a thermosetting functional group, the adhesive does not necessarily contain a thermosetting resin (epoxy resin or the like). The adhesive layer may have either a single-layer structure or a multi-layer structure.
Examples of the thermoplastic resin include: natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid ester copolymer, a polybutadiene resin, a polycarbonate resin, a thermoplastic polyimide resin, a polyamide resin such as 6-nylon and 6, 6-nylon, a phenoxy resin, an acrylic resin, a saturated polyester resin such as PET and PBT, a polyamideimide resin, a fluororesin, and the like. The thermoplastic resin may be used alone or in combination of two or more. The thermoplastic resin is preferably an acrylic resin because it has few ionic impurities and high heat resistance, and thus the bonding reliability by the adhesive layer is easily ensured.
The acrylic resin preferably contains a constituent unit derived from a hydrocarbon-containing (meth) acrylate as a constituent unit having the largest mass ratio. Examples of the hydrocarbon group-containing (meth) acrylate include: examples of the hydrocarbon group-containing (meth) acrylate that forms the hydrocarbon group-containing (meth) acrylate of the acrylic polymer that can be contained in the pressure-sensitive adhesive layer are hydrocarbon group-containing (meth) acrylates.
The acrylic resin may contain a constituent unit derived from another monomer component copolymerizable with the hydrocarbon group-containing (meth) acrylate. Examples of the other monomer components include: a carboxyl group-containing monomer; an acid anhydride monomer; a hydroxyl group-containing monomer; a glycidyl group-containing monomer; a sulfonic acid group-containing monomer; a phosphoric acid group-containing monomer; functional group-containing monomers such as acrylamide and acrylonitrile; specifically, the monomer components exemplified as the other monomer components constituting the acrylic polymer that can be contained in the pressure-sensitive adhesive layer can be used.
When the adhesive layer contains a thermoplastic resin and a thermosetting resin, examples of the thermosetting resin include: epoxy resins, phenol resins, amino resins, unsaturated polyester resins, polyurethane resins, silicone resins, thermosetting polyimide resins, and the like. The thermosetting resin may be used alone or in combination of two or more. An epoxy resin is preferable as the thermosetting resin because of a tendency that the content of ionic impurities and the like which may cause corrosion of a semiconductor chip to be die bonded is small. As the curing agent for the epoxy resin, a phenol resin is preferable.
Examples of the epoxy resin include: bisphenol a type, bisphenol F type, bisphenol S type, brominated bisphenol a type, hydrogenated bisphenol a type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, o-cresol novolac type, trishydroxyphenylmethane type, tetrakis (phenylhydroxy) ethane (Tetraphenylolethane) type, hydantoin type, triglycidyl isocyanurate type, glycidyl amine type epoxy resins, and the like. Among them, a novolak type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type epoxy resin, and a tetrakis (phenylhydroxy) ethane type epoxy resin are preferable because they are highly reactive with a phenolic resin as a curing agent and have excellent heat resistance.
Examples of the phenolic resin which can function as a curing agent for an epoxy resin include: and a novolak phenol resin, a resol phenol resin, and a polyoxyethylene such as a poly-p-oxystyrene. Examples of the novolak phenol resin include: phenol novolac resins, phenol aralkyl resins, cresol novolac resins, tert-butylphenol novolac resins, nonylphenol novolac resins, and the like. The phenol resin may be used alone or in combination of two or more. Among them, phenol novolac resins and phenol aralkyl resins are preferable from the viewpoint of increasing the connection reliability of an epoxy resin used as an adhesive for die bonding, when used as a curing agent for the adhesive.
In the adhesive layer, the phenolic resin is contained in an amount such that the hydroxyl group in the phenolic resin is preferably 0.5 to 2.0 equivalents, more preferably 0.7 to 1.5 equivalents, relative to 1 equivalent of the epoxy group in the epoxy resin component, from the viewpoint of sufficiently proceeding the curing reaction of the epoxy resin and the phenolic resin.
When the adhesive layer contains a thermosetting resin, the content of the thermosetting resin is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of the adhesive layer, from the viewpoint of allowing the adhesive layer to exhibit a function as a thermosetting adhesive.
When the adhesive layer contains a thermoplastic resin having a thermosetting functional group, an acrylic resin having a thermosetting functional group can be used as the thermoplastic resin, for example. The acrylic resin in the thermosetting functional group-containing acrylic resin preferably contains a constituent unit derived from a hydrocarbon group-containing (meth) acrylate as a constituent unit in the largest proportion by mass. Examples of the hydrocarbon group-containing (meth) acrylate include: the hydrocarbon group-containing (meth) acrylate is exemplified as a hydrocarbon group-containing (meth) acrylate forming the acrylic polymer that can be contained in the pressure-sensitive adhesive layer.
On the other hand, examples of the thermosetting functional group in the thermosetting functional group-containing acrylic resin include: glycidyl, carboxyl, hydroxyl, isocyanate, and the like. Among them, glycidyl group and carboxyl group are preferable. That is, as the acrylic resin having a thermosetting functional group, a glycidyl group-containing acrylic resin and a carboxyl group-containing acrylic resin are particularly preferable. In addition, it is preferable to contain a curing agent together with the thermosetting functional group-containing acrylic resin, and examples of the curing agent include: examples of the crosslinking agent that may be contained in the radiation curable pressure-sensitive adhesive for forming a pressure-sensitive adhesive layer include a crosslinking agent. When the thermosetting functional group in the thermosetting functional group-containing acrylic resin is a glycidyl group, a polyphenol compound is preferably used as the curing agent, and for example, the above-mentioned various phenol resins can be used.
In order to achieve a certain degree of crosslinking in the adhesive layer before curing for die bonding, for example, a polyfunctional compound capable of reacting with and bonding to a functional group at a molecular chain end of the resin which can be contained in the adhesive layer is preferably blended in advance as a crosslinking component in the resin composition for forming the adhesive layer. Such a configuration is preferable from the viewpoint of improving the adhesion properties of the adhesive layer at high temperatures and from the viewpoint of improving the heat resistance.
Examples of the crosslinking component include: a polyisocyanate compound. As the polyisocyanate compound, for example: toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, adducts of polyols and diisocyanates, and the like. In addition, as the crosslinking component, other polyfunctional compounds such as epoxy resin can be used in combination with the polyisocyanate compound.
The content of the crosslinking component in the resin composition for forming an adhesive layer is preferably 0.05 parts by mass or more in terms of improving the cohesive strength of the adhesive layer to be formed and preferably 7 parts by mass or less in terms of improving the adhesive strength of the adhesive layer to be formed, relative to 100 parts by mass of the resin having the functional group capable of reacting with and bonding to the crosslinking component.
The adhesive layer preferably contains a filler. By mixing the filler into the adhesive layer, physical properties such as conductivity, thermal conductivity, and elastic modulus of the adhesive layer can be adjusted. Examples of the filler include inorganic fillers and organic fillers, and inorganic fillers are particularly preferable.
Examples of the inorganic filler include: aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous silica; and simple metal substances and alloys such as aluminum, gold, silver, copper, nickel and the like; amorphous carbon black, graphite, and the like. The filler may have various shapes such as a spherical shape, a needle shape, and a flake shape. The filler may be used alone or in combination of two or more.
The average particle diameter of the filler is preferably 0.005 to 10 μm, more preferably 0.005 to 1 μm. When the average particle diameter is 0.005 μm or more, wettability and adhesiveness to an adherend such as a semiconductor wafer are further improved. When the average particle diameter is 10 μm or less, the effect of the filler added to impart the above-described characteristics can be sufficiently exhibited, and heat resistance can be ensured. The average particle diameter of the filler can be determined, for example, by using a photometric particle size distribution meter (for example, trade name "LA-910", manufactured by horiba, Ltd.).
The adhesive layer may contain other components as necessary. Examples of the other components include: curing catalysts, flame retardants, silane coupling agents, ion trapping agents, dyes, and the like. The other additives may be used alone or in combination of two or more.
Examples of the flame retardant include: antimony trioxide, antimony pentoxide, brominated epoxy resins, and the like.
Examples of the silane coupling agent include: beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, etc.
Examples of the ion scavenger include: hydrotalcite compounds, bismuth hydroxide, antimony oxide hydrate (for example, "IXE-300" manufactured by east asian synthesis corporation), zirconium phosphate having a specific structure (for example, "IXE-100" manufactured by east asian synthesis corporation), magnesium silicate (for example, "Kyoward 600" manufactured by synechiae chemical industry co., ltd.), aluminum silicate (for example, "Kyoward 700" manufactured by synechiae chemical industry co., ltd.), and the like.
As the ion scavenger, a compound capable of forming a complex with a metal ion may also be used. Examples of such compounds include: triazole compounds, tetrazole compounds, and bipyridine compounds. Among these, from the viewpoint of stability of a complex formed with a metal ion, a triazole-based compound is preferable.
Examples of the triazole compound include: 1,2, 3-benzotriazole, 1- { N, N-bis (2-ethylhexyl) aminomethyl } benzotriazole, carboxybenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 6- (2-benzotriazolyl) -4-tert-octyl-6 '-tert-butyl-4' -methyl-2, 2 ' -methylenebisphenol, 1- (2 ', 3 ' -hydroxypropyl) benzotriazole, 1- (1, 2-dicarboxydiethyl) benzotriazole, 1- (2-ethylhexylaminomethyl) benzotriazole, 2, 4-di-tert-amyl-6- { (H-benzotriazol-1-yl) methyl } phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, octyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, and mixtures thereof, 2-ethylhexyl 3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propanoate, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) -benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chloro-benzotriazole, 2- [ 2-hydroxy-3, 5-bis (1, 1-dimethylbenzyl) phenyl ] -2H-benzotriazole, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol ], 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl ] propane Acid methyl esters, and the like.
In addition, as the ion scavenger, a predetermined hydroxyl group-containing compound such as a hydroquinone compound, a hydroxyanthraquinone compound, a polyphenol compound, or the like may be used. Specific examples of such a hydroxyl group-containing compound include: 1, 2-benzenediol, alizarin, 1, 5-dihydroxy anthraquinone, tannic acid, gallic acid, methyl gallate, pyrogallol and the like.
The thickness of the adhesive layer (total thickness in the case of a laminate) is not particularly limited, and is, for example, 1 to 200 μm. The upper limit is preferably 100. mu.m, more preferably 80 μm. The lower limit is preferably 3 μm, more preferably 5 μm.
In the dicing die-bonding film of the present invention, the peel force between the pressure-sensitive adhesive layer and the adhesive layer in a T-peel test under the conditions of a temperature of 23 ℃ and a peel speed of 300 mm/min is preferably 0.3N/20mm or more, more preferably 0.5N/20mm or more, and still more preferably 0.7N/20mm or more. When the peel force is 0.3N/20mm or more, the adhesiveness between the pressure-sensitive adhesive layer and the adhesive layer can be made appropriate, and when the expansion step is performed in a state where the radiation curing is not performed, the occurrence of peeling (floating) between the pressure-sensitive adhesive layer and the adhesive layer in the expansion step and thereafter can be easily suppressed.
The higher the peeling force, the more preferable the upper limit thereof is, for example, 10N/20mm, 5.0N/20mm or 3.0N/20 mm. In the dicing die-bonding film using the radiation-curable pressure-sensitive adhesive in the pressure-sensitive adhesive layer, the above-mentioned peeling force of the pressure-sensitive adhesive layer before radiation curing (peeling force in the T-type peeling test before ultraviolet curing) is preferably the above-mentioned value.
In the dicing die-bonding film of the present invention, the peeling force between the pressure-sensitive adhesive layer and the adhesive layer after radiation curing in a T-peel test under the conditions of a temperature of 23 ℃ and a peeling speed of 300 mm/min is preferably 0.3N/20mm or less, more preferably 0.2N/20mm or less. When the peel force is 0.3N/20mm or less, good pickup can be easily achieved in the pickup step performed after the radiation curing.
The dicing die-bonding film may have a separator. Specifically, the dicing die-bonding film may have a sheet-like shape having a separator for each dicing die-bonding film, or may have a long separator, and a plurality of dicing die-bonding films may be arranged on the long separator and the separator may be wound into a roll.
The separator is an element for covering and protecting the surface of the adhesive layer of the dicing die-bonding film, and is peeled from the dicing die-bonding film when the film is used. Examples of the separator include: polyethylene terephthalate (PET) film, polyethylene film, polypropylene film, plastic film or paper coated with a release agent such as a fluorine-based release agent or an acrylic long-chain alkyl ester-based release agent. The thickness of the spacer is, for example, 5 to 200 μm.
The dicing die-bonding film 1 as one embodiment of the dicing die-bonding film of the present invention can be manufactured, for example, as follows.
First, the substrate 11 can be obtained by film-forming by a known or conventional film-forming method. Examples of the film forming method include a rolling film forming method, a casting method in an organic solvent, a blow extrusion method in a closed system, a T-die extrusion method, a coextrusion method, and a dry lamination method.
Then, a composition (adhesive composition) for forming the adhesive layer 12, including the adhesive and the solvent for forming the adhesive layer 12, is applied to the substrate 11 to form a coating film, and then the coating film is cured by desolvation, curing, or the like as necessary, thereby forming the adhesive layer 12. Examples of the coating method include known or conventional coating methods such as roll coating, screen coating, and gravure coating. The solvent removal is carried out, for example, at a temperature of 80 to 150 ℃ for 0.5 to 5 minutes.
Alternatively, the pressure-sensitive adhesive layer 12 may be formed by applying the pressure-sensitive adhesive composition to the separator to form a coating film, and then curing the coating film under the above-described desolvation conditions. Then, the adhesive layer 12 is bonded to the substrate 11 together with the separator. In the above operation, the dicing tape 10 can be manufactured. When the method of transferring the adhesive layer 12 formed on the separator to the substrate 11 is employed, it is preferable to use a separator having a release-treated surface (adhesive composition-coated surface) with a smaller Ra so that the Ra of the surface 12a of the adhesive layer 12 is 1.0 μm or less.
First, a composition (adhesive composition) for forming adhesive layer 20, which includes a resin, a filler, a curing catalyst, a solvent, and the like, is prepared for adhesive layer 20. Then, the adhesive composition is applied to the separator to form a coating film, and the coating film is cured by desolvation, curing, or the like as necessary to form the adhesive layer 20. The coating method is not particularly limited, and examples thereof include known or conventional coating methods such as roll coating, screen coating, and gravure coating. The solvent removal is carried out, for example, at a temperature of 70 to 160 ℃ for 1 to 5 minutes.
Subsequently, the separator is peeled from the dicing tape 10 and the adhesive layer 20, and the adhesive layer 20 and the pressure-sensitive adhesive layer 12 are bonded to each other so as to form a bonding surface. The bonding may be performed by, for example, crimping. In this case, the laminating temperature is not particularly limited, and is, for example, preferably 30 to 50 ℃ and more preferably 35 to 45 ℃. The linear pressure is not particularly limited, but is, for example, preferably 0.1 to 20kgf/cm, more preferably 1 to 10 kgf/cm.
As described above, in the case where the pressure-sensitive adhesive layer 12 is a radiation-curable pressure-sensitive adhesive layer, when the pressure-sensitive adhesive layer 12 is irradiated with radiation such as ultraviolet rays after the bonding of the pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 12 is irradiated with radiation from the base material 11 side, for example, in an amount of 50 to 500mJ, preferably 100 to 300 mJ.
The region (irradiation region R) of the dicing die-bonding film 1 to which irradiation as a measure for reducing the adhesive strength of the adhesive layer 12 is performed is usually a region other than the edge portion of the bonding region of the adhesive layer 20 in the adhesive layer 12. When the irradiation region R is locally provided, the irradiation region R may be provided through a photomask on which a pattern corresponding to a region other than the irradiation region R is formed. Further, a method of forming the irradiation region R by spot-like irradiation with radiation may be mentioned.
In the above operation, the dicing die-bonding film 1 shown in fig. 1, for example, can be produced.
[ method for manufacturing semiconductor device ]
The dicing die-bonding film of the present invention can be used to manufacture a semiconductor device. Specifically, the semiconductor device can be manufactured by a manufacturing method including the steps of: a step (which may be referred to as "step a") of attaching a semiconductor wafer divided body including a plurality of semiconductor chips or a semiconductor wafer capable of being singulated into a plurality of semiconductor chips to the adhesive layer side in the dicing die-bonding film of the present invention; a step of spreading the dicing tape in the dicing die-bonding film of the invention under a relatively low temperature condition to cleave at least the adhesive layer to obtain a semiconductor chip with an adhesive layer (sometimes referred to as "step B"); a step (sometimes referred to as "step C") of spreading the dicing tape under a relatively high temperature condition to widen the interval between the semiconductor chips with the adhesive layer; and a step (sometimes referred to as "step D") of picking up the semiconductor chip with the adhesive layer.
The divided body of the semiconductor wafer including the plurality of semiconductor chips or the semiconductor wafer capable of being singulated into the plurality of semiconductor chips used in the step a can be obtained as follows. First, as shown in fig. 2a and 2 b, the dividing grooves 30a are formed in the semiconductor wafer W (dividing groove forming step). The semiconductor wafer W has a 1 st surface Wa and a 2 nd surface Wb. Various semiconductor elements (not shown) are already mounted on the 1 st surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) required for the semiconductor elements are also already formed on the 1 st surface Wa.
Then, after the wafer processing tape T1 having the adhesive surface T1a is bonded to the 2 nd surface Wb side of the semiconductor wafer W, the dicing groove 30a having a predetermined depth is formed on the 1 st surface Wa side of the semiconductor wafer W by using a rotary cutter such as a dicing device in a state where the semiconductor wafer W is held on the wafer processing tape T1. The dividing grooves 30a are gaps for separating the semiconductor wafer W into semiconductor chip units (the dividing grooves 30a are schematically shown by thick lines in fig. 2 to 4).
Then, as shown in fig. 2 (c), the wafer processing tape T2 having the adhesive surface T2a is bonded to the 1 st surface Wa side of the semiconductor wafer W, and the wafer processing tape T1 is peeled from the semiconductor wafer W.
Then, as shown in fig. 2 d, the semiconductor wafer W is thinned to a predetermined thickness by grinding from the 2 nd surface Wb in a state where the semiconductor wafer W is held on the wafer processing tape T2 (wafer thinning step). The grinding process may be performed using a grinding apparatus having a grinding stone. Through this wafer thinning step, the semiconductor wafer 30A that can be singulated into a plurality of semiconductor chips 31 can be formed in the present embodiment.
Specifically, the semiconductor wafer 30A has a portion (connection portion) where portions to be singulated into the plurality of semiconductor chips 31 are connected on the 2 nd surface Wb side. The thickness of the connecting portion of the semiconductor wafer 30A, i.e., the distance between the 2 nd surface Wb of the semiconductor wafer 30A and the tip of the dividing groove 30A on the 2 nd surface Wb side is, for example, 1 to 30 μm, preferably 3 to 20 μm.
(Process A)
In step a, a semiconductor wafer divided body including a plurality of semiconductor chips or a semiconductor wafer capable of being singulated into a plurality of semiconductor chips is attached to the dicing die-bonding film 1 on the adhesive layer 20 side.
In one embodiment of step a, as shown in fig. 3 (a), the semiconductor wafer 30A held by the wafer processing tape T2 is bonded to the adhesive layer 20 of the dicing die-bonding film 1. Then, as shown in fig. 3 (b), the wafer processing tape T2 is peeled from the semiconductor wafer 30A.
After the semiconductor wafer 30A is bonded to the adhesive layer 20, the pressure-sensitive adhesive layer 12 is irradiated with radiation such as ultraviolet rays from the base material 11 side. The irradiation amount is, for example, 50 to 500mJ/cm2Preferably 100 to 300mJ/cm2. The region (irradiation region R shown in fig. 1) of the dicing die-bonding film 1 to be irradiated as a measure for reducing the adhesive strength of the adhesive layer 12 is, for example, the adhesive layer 2 of the adhesive layer 120 region excluding the edge portion thereof.
(Process B)
In step B, the dicing tape 10 in the dicing die-bonding film 1 is spread at a relatively low temperature to cut at least the adhesive layer 20, thereby obtaining a semiconductor chip with an adhesive layer.
In one embodiment of step B, the ring frame 41 is first attached to the adhesive layer 12 of the dicing tape 10 in the dicing die-bonding film 1, and then the dicing die-bonding film 1 with the semiconductor wafer 30A is fixed to the holder 42 of the expanding device as shown in fig. 4 (a).
Then, as shown in fig. 4 (b), the first expanding step (cold expanding step) under relatively low temperature conditions is performed to singulate the semiconductor wafer 30A into a plurality of semiconductor chips 31 and to cut the adhesive layer 20 of the dicing die bonding film 1 into small adhesive layers 21, thereby obtaining the semiconductor chips 31 with adhesive layers.
In the cold spreading step, the hollow cylindrical jacking member 43 provided in the spreading device is brought into contact with the dicing tape 10 on the lower side of the dicing die-bonding film 1 in the drawing and is raised, and the dicing tape 10 of the dicing die-bonding film 1 to which the semiconductor wafer 30A is bonded is spread so as to be stretched in the two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer 30A.
The expansion is performed under conditions such that a tensile stress in the range of 15 to 32MPa, preferably 20 to 32MPa is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, 0 ℃ or lower, preferably-20 to-5 ℃, more preferably-15 to-5 ℃, and still more preferably-15 ℃. The expansion rate (speed for raising the jack-up member 43) in the cold expansion step is preferably 0.1 to 100 mm/sec. The amount of expansion in the cold expansion step is preferably 3 to 16 mm.
When the semiconductor wafer 30A capable of being singulated into a plurality of semiconductor chips is used in the step B, the semiconductor wafer 30A is cut at a thin portion where cracks are likely to occur, and is singulated into the semiconductor chips 31. At the same time, in the step B, the adhesive layer 20 adhering to the adhesive layer 12 of the expanded dicing tape 10 is suppressed from being deformed in each region where the semiconductor chips 31 adhere to each other, and such deformation suppression is not generated at a position located in a direction perpendicular to the dividing groove between the semiconductor chips 31 in the drawing, and the tensile stress generated in the dicing tape 10 acts in this state. As a result, the adhesive layer 20 is cut at a position in the direction perpendicular to the dividing groove between the semiconductor chips 31. After the cutting by the expansion, as shown in fig. 4 (c), the jack member 43 is lowered to release the expanded state of the dicing tape 10.
(Process C)
In step C, the dicing tape 10 is spread under a relatively high temperature condition to widen the interval between the semiconductor chips with the adhesive layer.
In one embodiment of step C, first, as shown in fig. 5 (a), a 2 nd expanding step (room temperature expanding step) under relatively high temperature conditions is performed to widen the distance (spacing distance) between the semiconductor chips 31 with the adhesive layer.
In step C, the hollow cylindrical jacking member 43 provided in the expanding device is raised again to expand the dicing tape 10 for dicing the die-bonding film 1. The temperature in the second expansion step 2 is, for example, 10 ℃ or higher, preferably 15 to 30 ℃. The expanding speed (speed for raising the jack-up member 43) in the 2 nd expanding step is, for example, 0.1 to 10 mm/sec, preferably 0.3 to 1 mm/sec. In step C, the distance between the semiconductor chips 31 with the adhesive layer is increased to such an extent that the semiconductor chips 31 with the adhesive layer can be picked up from the dicing tape 10 in a pickup step described later. After the distance is widened by the expansion, the jack member 43 is lowered as shown in fig. 5 (b), and the expanded state of the dicing tape 10 is released.
From the viewpoint of suppressing the narrowing of the distance between the semiconductor chips 31 with the adhesive layer on the dicing tape 10 after the expanded state is released, it is preferable to heat and shrink the outer portion of the semiconductor chip 31 holding region in the dicing tape 10 before the expanded state is released.
After the step C, there may be provided a cleaning step of cleaning the semiconductor chip 31 side of the dicing tape 10 having the semiconductor chip 31 with the adhesive layer with a cleaning liquid such as water, if necessary.
(Process D)
In step D (pickup step), the singulated semiconductor chips with the adhesive layer are picked up. In one embodiment of step D, after the cleaning step as necessary, the semiconductor chip 31 with the adhesive layer is picked up from the dicing tape 10 as shown in fig. 6. For example, the semiconductor chip 31 with the adhesive layer to be picked up is lifted up via the dicing tape 10 by raising the needle member 44 of the pickup mechanism at the lower side of the dicing tape 10 in the drawing, and then is sucked and held by the suction jig 45. In the picking-up step, the needle member 44 is pushed up at a speed of, for example, 1 to 100 mm/sec and the needle member 44 is pushed up at a height of, for example, 50 to 3000 μm.
The method of manufacturing a semiconductor device may further include a step other than the steps a to D. For example, in one embodiment, as shown in fig. 7 (a), the picked-up semiconductor chip 31 with the adhesive layer is temporarily fixed to the adherend 51 via the adhesive layer 21 (temporary fixing step).
Examples of the adherend 51 include: lead frames, TAB (Tape automated bonding) films, wiring substrates, separately fabricated semiconductor chips, and the like. The shear adhesion strength of the adhesive layer 21 at 25 ℃ at the time of temporary fixing is preferably 0.2MPa or more, more preferably 0.2 to 10MPa, to the adherend 51. The configuration in which the shear adhesion force of the adhesive layer 21 is 0.2MPa or more can suppress shear deformation of the adhesive surface of the adhesive layer 21 and the semiconductor chip 31 or the adherend 51 caused by ultrasonic vibration or heating in the wire bonding step described later, and can suitably perform wire bonding. The shear adhesion strength of the adhesive layer 21 at 175 ℃ during temporary fixation is preferably 0.01MPa or more, and more preferably 0.01 to 5MPa, with respect to the adherend 51.
Then, as shown in fig. 7 b, the electrode pad (not shown) of the semiconductor chip 31 and the terminal portion (not shown) of the adherend 51 are electrically connected by the bonding wire 52 (wire bonding step).
The connection of the electrode pad of the semiconductor chip 31, the terminal portion of the adherend 51, and the bonding wire 52 can be achieved by ultrasonic welding with heating, and is performed so that the adhesive layer 21 is not thermally cured. As the bonding wire 52, for example, a gold wire, an aluminum wire, a copper wire, or the like can be used. The heating temperature of the wire in the wire bonding is, for example, 80 to 250 ℃, preferably 80 to 220 ℃. In addition, the heating time is several seconds to several minutes.
Then, as shown in fig. 7 c, the semiconductor chip 31 is sealed with a sealing resin 53 for protecting the semiconductor chip 31 and the bonding wire 52 on the adherend 51 (sealing step).
In the sealing step, the adhesive layer 21 is thermally cured. In the sealing step, the sealing resin 53 is formed by, for example, a transfer molding technique using a mold. As a constituent material of the sealing resin 53, for example, an epoxy resin can be used. In the sealing step, the heating temperature for forming the sealing resin 53 is, for example, 165 to 185 ℃, and the heating time is, for example, 60 seconds to several minutes.
When the sealing resin 53 is not sufficiently cured in the sealing step, a post-curing step for completely curing the sealing resin 53 is performed after the sealing step. Even when the adhesive layer 21 is not completely heat-cured in the sealing step, the adhesive layer 21 may be completely heat-cured together with the sealing resin 53 in the post-curing step. In the post-curing step, the heating temperature is, for example, 165 to 185 ℃, and the heating time is, for example, 0.5 to 8 hours.
In the above embodiment, as described above, after the semiconductor chip 31 with the adhesive layer is temporarily fixed to the adherend 51, the wire bonding step is performed in a state where the adhesive layer 21 is not completely thermally cured. Instead of this configuration, in the above-described method for manufacturing a semiconductor device, the adhesive layer-attached semiconductor chip 31 may be temporarily fixed to the adherend 51, and then the adhesive layer 21 may be thermally cured and then the wire bonding step may be performed.
In the method for manufacturing a semiconductor device, as another embodiment, a wafer thinning step shown in fig. 8 may be performed instead of the wafer thinning step described above with reference to fig. 2 (d). After the above-described process with reference to fig. 2 (c), in the wafer thinning step shown in fig. 8, the semiconductor wafer W is thinned to a predetermined thickness by grinding from the 2 nd surface Wb in a state where the semiconductor wafer W is held on the wafer processing tape T2, and the semiconductor wafer divided bodies 30B including the plurality of semiconductor chips 31 and held on the wafer processing tape T2 are formed.
In the wafer thinning step, the wafer may be ground until the dividing groove 30a is exposed on the 2 nd surface Wb side (method 1), or the following method may be used: the wafer is ground from the 2 nd surface Wb side to just before the dividing groove 30a, and then a pressing force of the rotary grindstone against the wafer is applied to crack between the dividing groove 30a and the 2 nd surface Wb, thereby forming a semiconductor wafer divided body 30B (method 2). The depth from the 1 st surface Wa of the dividing groove 30a formed as described above with reference to fig. 2 (a) and 2 (b) is determined as appropriate depending on the method used.
Fig. 8 schematically shows the dividing groove 30a formed by the method 1 or the dividing groove 30a formed by the method 2 and the crack connected thereto by a thick line. In the above-described method for manufacturing a semiconductor device, the steps described above with reference to fig. 3 to 7 may be performed using the semiconductor wafer segment 30B thus produced as a semiconductor wafer segment in the step a instead of the semiconductor wafer 30A.
Fig. 9 (a) and 9 (B) show step B of this embodiment, that is, step 1 (cold spreading step) performed after the semiconductor wafer segment 30B is bonded to the dicing die-bonding film 1.
In step B of this embodiment, the hollow cylindrical jacking member 43 provided in the expanding device is brought into contact with the dicing tape 10 on the lower side of the dicing die-bonding film 1 in the drawing and is raised, and the dicing tape 10 of the dicing die-bonding film 1 to which the semiconductor wafer segments 30B are bonded is expanded so as to be stretched in the two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer segments 30B.
The expansion is performed under conditions such that a tensile stress in the range of, for example, 5 to 28MPa, preferably 8 to 25MPa is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, 0 ℃ or lower, preferably-20 to-5 ℃, more preferably-15 to-5 ℃, and still more preferably-15 ℃. The expansion rate (speed for raising the jack-up member 43) in the cold expansion step is preferably 1 to 400 mm/sec. The amount of expansion in the cold expansion step is preferably 50 to 200 mm.
By the cold spreading step, the adhesive layer 20 of the dicing die-bonding film 1 is cut into small adhesive layers 21, and the semiconductor chip 31 with an adhesive layer is obtained. Specifically, in the cold expanding step, in the adhesive layer 20 that adheres to the adhesive layer 12 of the dicing tape 10 to be expanded, deformation is suppressed in each region where each semiconductor chip 31 of the semiconductor wafer divided body 30B adheres, while such a deformation suppressing action is not generated at a position located in a direction perpendicular to the dividing groove 30a between the semiconductor chips 31 in the drawing, and the tensile stress generated in the dicing tape 10 in this state acts. As a result, the adhesive layer 20 is cut at a position in the direction perpendicular to the dividing groove 30a between the semiconductor chips 31 in the figure.
In the above-described method for manufacturing a semiconductor device, as still another embodiment, a semiconductor wafer 30C produced as follows may be used instead of the semiconductor wafer 30A or the semiconductor wafer divided bodies 30B used in the step a.
In this embodiment, as shown in fig. 10 (a) and 10 (b), first, the modified region 30b is formed in the semiconductor wafer W. The semiconductor wafer W has a 1 st surface Wa and a 2 nd surface Wb. Various semiconductor elements (not shown) have been already mounted on the 1 st surface Wa side of the semiconductor wafer W, and wiring structures and the like (not shown) required for the semiconductor elements have also been formed on the 1 st surface Wa.
Then, after the wafer processing tape T3 having the adhesive surface T3a is bonded to the 1 st surface Wa side of the semiconductor wafer W, the semiconductor wafer W is irradiated with laser light having a focal point located inside the wafer from the side opposite to the wafer processing tape T3 along the pre-dividing line in a state where the semiconductor wafer W is held on the wafer processing tape T3, and the modified region 30b is formed in the semiconductor wafer W by ablation due to multiphoton absorption. The modified region 30b is a weakened region for separating the semiconductor wafer W into semiconductor chip units.
A method of forming the modified regions 30b on the preliminary dividing lines in the semiconductor wafer by laser irradiation is described in detail in, for example, japanese patent application laid-open No. 2002-192370, and the laser irradiation conditions in this embodiment can be appropriately adjusted within the following ranges, for example.
< laser irradiation conditions >
(A) Laser
Figure BDA0002453576670000361
(B) Lens for condensing light
Multiplying power of 100 times or less
NA 0.55
Transmittance to laser wavelength of 100% or less
(C) The moving speed of the mounting table for mounting the semiconductor substrate is below 280 mm/s
Then, as shown in fig. 10C, the semiconductor wafer W is thinned to a predetermined thickness by grinding from the 2 nd surface Wb in a state where the semiconductor wafer W is held on the wafer processing tape T3, thereby forming a semiconductor wafer 30C which can be singulated into a plurality of semiconductor chips 31 (wafer thinning step).
In the above-described method for manufacturing a semiconductor device, in the step a, the semiconductor wafer 30C thus produced may be used as a semiconductor wafer capable of being singulated instead of the semiconductor wafer 30A, and the above-described steps with reference to fig. 3 to 7 may be performed.
Fig. 11 (a) and 11 (B) show a step B in this embodiment, that is, a 1 st expanding step (cold expanding step) performed after the semiconductor wafer 30C is bonded to the dicing die-bonding film 1.
In the cold spreading step, the hollow cylindrical jacking member 43 provided in the spreading device is brought into contact with the dicing tape 10 on the lower side of the dicing die-bonding film 1 in the drawing and is raised, and the dicing tape 10 of the dicing die-bonding film 1 to which the semiconductor wafer 30C is bonded is spread so as to be stretched in the two-dimensional direction including the radial direction and the circumferential direction of the semiconductor wafer 30C.
The expansion is performed under conditions such that a tensile stress in the range of, for example, 5 to 28MPa, preferably 8 to 25MPa is generated in the dicing tape 10. The temperature condition in the cold expansion step is, for example, 0 ℃ or lower, preferably-20 to-5 ℃, more preferably-15 to-5 ℃, and still more preferably-15 ℃. The expansion rate (speed for raising the jack-up member 43) in the cold expansion step is preferably 1 to 400 mm/sec. The amount of expansion in the cold expansion step is preferably 50 to 200 mm.
By the cold spreading step, the adhesive layer 20 of the dicing die-bonding film 1 is cut into small adhesive layers 21, and the semiconductor chip 31 with an adhesive layer is obtained. Specifically, in the cold expansion step, cracks are formed in the fragile modified region 30b in the semiconductor wafer 30C, and the semiconductor chips 31 are singulated. At the same time, in the cold-expanding step, in the adhesive layer 20 that adheres to the adhesive layer 12 of the dicing tape 10 to be expanded, deformation is suppressed in each region where each semiconductor chip 31 of the semiconductor wafer 30C adheres, while such a deformation suppressing action is not generated at a position in the direction perpendicular to the crack formation position of the wafer in the drawing, and the tensile stress generated in the dicing tape 10 in this state acts. As a result, the adhesive layer 20 is cut at a position in the direction perpendicular to the crack formation position between the semiconductor chips 31 in the figure.
In the method for manufacturing a semiconductor device, the dicing die-bonding film 1 can be used in applications in which a semiconductor chip with an adhesive layer is to be obtained as described above, and can also be used in applications in which a semiconductor chip with an adhesive layer is obtained when a plurality of semiconductor chips are stacked and mounted in 3 dimensions. The semiconductor chips 31 mounted in 3-dimensional manner may or may not be provided with a spacer interposed therebetween together with the adhesive layer 21.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examplesThe examples are given in any way. The constituent acrylic polymers P of the pressure-sensitive adhesive layers in examples and comparative examples were2The composition of each monomer component (2) is shown in the table. In the table, the unit of each numerical value indicating the composition of the composition indicates the relative "mole" of the monomer component in the composition, and the unit of each numerical value other than the monomer component indicates the relative "mole" of the monomer component in the composition, and the unit of each numerical value indicates the relative "mole" of the monomer component in the acrylic polymer P2100 parts by mass of "parts by mass".
Example 1
(cutting tape)
In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirring device, a mixture containing 100 moles of 2-ethylhexyl acrylate (2EHA), 30 moles of 2-hydroxyethyl acrylate (HEA), 30 moles of Acryloyl Morpholine (AM), 0.2 parts by mass of benzoyl peroxide as a polymerization initiator per 100 parts by mass of these monomer components, and toluene as a polymerization solvent was stirred (polymerization reaction) at 61 ℃ for 6 hours under a nitrogen atmosphere. Thus, an acrylic-containing polymer P was obtained1The polymer solution of (1).
Then, the acrylic acid-containing polymer P is contained1The mixture of the polymer solution of (1), 2-methacryloyloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was stirred at 50 ℃ for 48 hours under an air atmosphere (addition reaction). The MOI content in the reaction solution was 25 mol. In addition, in the reaction solution, the amount of dibutyltin dilaurate added was based on the acrylic polymer P1100 parts by mass is 0.01 part by mass. The addition reaction gives an acrylic polymer P having a methacrylate group in the side chain2(acrylic polymer containing constituent units derived from an unsaturated functional group-containing isocyanate compound).
Then, the acrylic polymer P was added to the polymer solution2100 parts by mass of 1 part by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Corp.), and 2 parts by mass of a photopolymerizable compoundAn initiator (trade name "Irgacure 127", manufactured by BASF) was mixed, and toluene was added thereto to dilute the mixture, thereby obtaining an adhesive composition.
Then, an adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 50 μm) having the silicone release-treated surface using an applicator to form an adhesive composition layer. Then, the composition layer was subjected to desolvation based on heating at 120 ℃ for 2 minutes to form an adhesive layer having a thickness of 10 μm on the PET separator.
Then, an EVA film (thickness 125 μm) as a base material was laminated on the exposed surface of the pressure-sensitive adhesive layer at room temperature using a laminator. The laminate was then stored at 50 ℃ for 24 hours. The dicing tape of example 1 was produced in the manner described above.
(adhesive layer)
Mixing acrylic polymer A1(a copolymer of ethyl acrylate, butyl acrylate, acrylonitrile and glycidyl methacrylate, having a mass-average molecular weight of 120 ten thousand, a glass transition temperature of 0 ℃ and an epoxy value of 0.4eq/kg), 54 parts by mass of a solid phenol resin (trade name "MEHC-7851 SS", manufactured by kayaku chemical corporation, solid at 23 ℃), 3 parts by mass of a liquid phenol resin (trade name "MEH-8000H", manufactured by kayaku chemical corporation, liquid at 23 ℃), and 40 parts by mass of a silica filler (trade name "SO-C2", manufactured by kayaku chemical corporation, admimhs co., ltd.) were added to methyl ethyl ketone and mixed, and the concentration was adjusted SO that the viscosity at room temperature became 700mPa · s, to obtain an adhesive composition.
Then, an adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 38 μm) having the silicone release-treated surface using an applicator to form a coating film, and the coating film was desolventized at 130 ℃ for 2 minutes. The adhesive layer of 10 μm thickness in example 1 was formed on the PET separator in the manner described above.
(preparation of dicing die-bonding film)
The PET separator was peeled from the dicing tape of example 1, and the adhesive layer of example 1 was adhered to the exposed adhesive layer. During the bonding, a hand press roller is used. Then, 300mJ of ultraviolet light was irradiated from the dicing tape side to produce a dicing die-bonding film of example 1.
Example 2
The acrylic polymer P constituting the pressure-sensitive adhesive layer2A dicing tape and a dicing die-bonding film of example 2 were produced in the same manner as in example 1, except that the blending amount of Acryloyl Morpholine (AM) (an acrylic polymer containing a structural unit derived from an unsaturated functional group-containing isocyanate compound) was changed to 10 moles.
Example 3
A dicing tape and a dicing die-bonding film of example 3 were produced in the same manner as in example 1, except that the pressure-sensitive adhesive layer was not irradiated with ultraviolet rays.
Example 4
The dicing tape and the dicing die-bonding film of example 4 were produced in the same manner as in example 3, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 2 parts by mass in the production of the pressure-sensitive adhesive layer.
Example 5
A dicing tape and a dicing die-bonding film of example 5 were produced in the same manner as in example 2, except that the pressure-sensitive adhesive layer was not irradiated with ultraviolet rays.
Example 6
The dicing tape and the dicing die-bonding film of example 6 were produced in the same manner as in example 5, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 2 parts by mass in the production of the pressure-sensitive adhesive layer.
Example 7
(cutting tape)
In a reaction vessel equipped with a condenser tube, a nitrogen inlet tube, a thermometer, and a stirring device, benzoyl peroxide as a polymerization initiator was added in an amount of 0.2 parts by mass per 100 parts by mass of the monomer components, the amount being 50 moles of Ethyl Acrylate (EA), 50 moles of Butyl Acrylate (BA), and 20 moles of 2-hydroxyethyl acrylate (HEA)And toluene as a polymerization solvent were stirred at 61 ℃ for 6 hours under a nitrogen atmosphere (polymerization reaction). Thus, an acrylic-containing polymer P was obtained1The polymer solution of (1).
Then, the acrylic acid-containing polymer P is contained1The mixture of the polymer solution of (1), 2-methacryloyloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was stirred at 50 ℃ for 48 hours under an air atmosphere (addition reaction). The MOI content in the reaction solution was 18 mol. In addition, in the reaction solution, the amount of dibutyltin dilaurate added was based on the acrylic polymer P1100 parts by mass is 0.01 part by mass. The addition reaction gives an acrylic polymer P having a methacrylate group in the side chain2(acrylic polymer containing structural units derived from an unsaturated functional group-containing isocyanate compound).
Then, the acrylic polymer P was added to the polymer solution2100 parts by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) and 2 parts by mass of a photopolymerization initiator (trade name "Irgacure 127", manufactured by BASF) were mixed, and then diluted with toluene to obtain an adhesive composition.
Then, an adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 50 μm) having the silicone release-treated surface using an applicator to form an adhesive composition layer. Then, the composition layer was subjected to desolvation based on heating at 120 ℃ for 2 minutes to form an adhesive layer having a thickness of 10 μm on the PET separator.
Then, an EVA film (thickness 125 μm) as a base material was laminated on the exposed surface of the pressure-sensitive adhesive layer at room temperature using a laminator. The laminate was then stored at 50 ℃ for 24 hours. The dicing tape of example 7 was produced in the same manner as described above.
(preparation of dicing die-bonding film)
The PET separator was peeled from the dicing tape of example 7, and the adhesive layer of example 1 was adhered to the exposed adhesive layer. During the bonding, a hand press roller is used. In this manner, a dicing die-bonding film of example 7 was produced.
Example 8
The dicing tape and the dicing die-bonding film of example 8 were produced in the same manner as in example 7, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 2 parts by mass in the production of the pressure-sensitive adhesive layer.
Comparative example 1
(cutting tape)
In a reaction vessel equipped with a condenser, a nitrogen inlet tube, a thermometer, and a stirring device, a mixture containing 100 moles of 2-ethylhexyl acrylate (2EHA), 20 moles of 2-hydroxyethyl acrylate (HEA), 0.2 parts by mass of benzoyl peroxide as a polymerization initiator per 100 parts by mass of these monomer components, and toluene as a polymerization solvent was stirred (polymerization reaction) at 61 ℃ for 6 hours under a nitrogen atmosphere. Thus, an acrylic-containing polymer P was obtained1The polymer solution of (1).
Then, the acrylic acid-containing polymer P is contained1The mixture of the polymer solution of (1), 2-methacryloyloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was stirred at 50 ℃ for 48 hours under an air atmosphere (addition reaction). The MOI content in the reaction solution was 18 mol. In addition, in the reaction solution, the amount of dibutyltin dilaurate added was based on the acrylic polymer P1100 parts by mass is 0.01 part by mass. The addition reaction gives an acrylic polymer P having a methacrylate group in the side chain2(acrylic polymer containing structural units derived from an unsaturated functional group-containing isocyanate compound).
Then, the acrylic polymer P was added to the polymer solution2100 parts by mass of 0.5 part by mass of polyisocyanate compound (trade name "CORONATE L", manufactured by Tosoh Corp.), and 2 parts by mass of photopolymerization initiator(trade name "Irgacure 127", manufactured by BASF corporation) and mixed, and further, toluene was added thereto to dilute the mixture, thereby obtaining an adhesive composition.
Then, an adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 50 μm) having the silicone release-treated surface using an applicator to form an adhesive composition layer. Then, the composition layer was subjected to desolvation based on heating at 120 ℃ for 2 minutes to form an adhesive layer having a thickness of 10 μm on the PET separator.
Then, an EVA film (thickness 125 μm) as a base material was laminated on the exposed surface of the pressure-sensitive adhesive layer at room temperature using a laminator. The laminate was then stored at 50 ℃ for 24 hours. The dicing tape of comparative example 1 was produced in the manner described above.
(preparation of dicing die-bonding film)
The PET separator was peeled from the dicing tape of comparative example 1, and the adhesive layer of example 1 was adhered to the exposed adhesive layer. During the bonding, a hand press roller is used. In this manner, the dicing die-bonding film of comparative example 1 was produced.
Comparative example 2
A dicing tape and a dicing die-bonding film of comparative example 2 were produced in the same manner as in comparative example 1, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 1 part by mass in the production of the pressure-sensitive adhesive layer.
Comparative example 3
A dicing tape and a dicing die-bonding film of comparative example 3 were produced in the same manner as in comparative example 1, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 2 parts by mass in the production of the pressure-sensitive adhesive layer.
Comparative example 4
(cutting tape)
In a reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirring device, 100 moles of Lauryl Methacrylate (LMA) and 20 moles of 2-hydroxyethyl methacrylate (HEMA) were added, and the amount of the components was 0.2 parts by mass per 100 parts by mass of the monomer componentsA mixture of parts of benzoyl peroxide as a polymerization initiator and toluene as a polymerization solvent was stirred at 61 ℃ for 6 hours under a nitrogen atmosphere (polymerization reaction). Thus, an acrylic-containing polymer P was obtained1The polymer solution of (1).
Then, the acrylic acid-containing polymer P is contained1The mixture of the polymer solution of (1), 2-methacryloyloxyethyl isocyanate (MOI), and dibutyltin dilaurate as an addition reaction catalyst was stirred at 50 ℃ for 48 hours under an air atmosphere (addition reaction). The MOI content in the reaction solution was 18 mol. In addition, in the reaction solution, the amount of dibutyltin dilaurate added was based on the acrylic polymer P1100 parts by mass is 0.01 part by mass. The addition reaction gives an acrylic polymer P having a methacrylate group in the side chain2(acrylic polymer containing structural units derived from an unsaturated functional group-containing isocyanate compound).
Then, the acrylic polymer P was added to the polymer solution2100 parts by mass of a polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) and 2 parts by mass of a photopolymerization initiator (trade name "Irgacure 127", manufactured by BASF) were mixed, and then diluted with toluene to obtain an adhesive composition.
Then, an adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 50 μm) having the silicone release-treated surface using an applicator to form an adhesive composition layer. Then, the composition layer was subjected to desolvation based on heating at 120 ℃ for 2 minutes to form an adhesive layer having a thickness of 10 μm on the PET separator.
Then, an EVA film (thickness 125 μm) as a base material was laminated on the exposed surface of the pressure-sensitive adhesive layer at room temperature using a laminator. The laminate was then stored at 50 ℃ for 24 hours. The dicing tape of comparative example 4 was produced in the manner described above.
(preparation of dicing die-bonding film)
The PET separator was peeled from the dicing tape of comparative example 4, and the adhesive layer of example 1 was adhered to the exposed adhesive layer. During the bonding, a hand press roller is used. In this manner, the dicing die-bonding film of comparative example 4 was produced.
Comparative example 5
A dicing tape and a dicing die-bonding film of comparative example 5 were produced in the same manner as in comparative example 4, except that the amount of polyisocyanate compound (trade name "CORONATE L", manufactured by tokyo co., ltd.) was changed to 1 part by mass in the production of the pressure-sensitive adhesive layer.
Comparative example 6
In the production of the pressure-sensitive adhesive layer, a dicing tape and a dicing die-bonding film of comparative example 6 were produced in the same manner as in example 2 except that the pressure-sensitive adhesive composition was applied to the silicone release-treated surface of the PET separator (thickness 50 μm, arithmetic mean surface roughness of the release-treated surface 1.0 μm) having the silicone release-treated surface by using an applicator to form the pressure-sensitive adhesive composition layer.
< evaluation >
The dicing die-bonding films obtained in examples and comparative examples were evaluated as follows. The results are shown in the table.
(1) Surface roughness
The dicing die-bonding films obtained in examples and comparative examples were subjected to surface measurement of the adhesive layer in the region where the adhesive layer was not laminated, and arithmetic mean surface roughness (Ra) was measured at a magnification of 10 times that of an eyepiece and 20 times that of an objective lens using a laser confocal microscope (trade name "shape measurement laser microscope VK-X100", manufactured by keyence corporation).
(2) Water contact angle
The water contact angle was measured by dropping 1 drop of a reagent onto the surface of the pressure-sensitive adhesive layer using a contact angle meter "CA-X" (manufactured by synechia-interfacial science) and measuring the angle at that time.
(3) Value of polar component of surface free energy obtained from Kaelble Uy equation
The same procedure as the measurement of the water contact angle was carried out to measure the diiodomethane contact on the surface of the pressure-sensitive adhesive layerAnd (4) an angle. Then, the contact angle of water measured in the contact angle evaluation is represented by θ w, and the contact angle of diiodomethane is represented by θ i, and γ s is obtained from the following equations (2) and (3)pAs the value of the polar component of the surface free energy. Note that γ w is 72.8mJ/m2,γwdIs 21.8mJ/m2,γwpIs 51.0mJ/m2And gamma i is 50.8mJ/m2,γidIs 48.5mJ/m2,γipIs 2.3mJ/m2
γw(1+cosθw)=2(γsdγwd)1/2+2(γspγwp)1/2(2)
γi(1+cosθi)=2(γsdγid)1/2+2(γspγip)1/2(3)
(4) Lifting of semiconductor chip with chip joint film
A trade name "ML 300-Integration" (manufactured by tokyo co., ltd.) was used as a laser processing apparatus, and a modified region was formed inside a semiconductor wafer by irradiating laser light along a pre-dividing line in a lattice shape (10mm × 10mm) with a light converging point aligned inside a 12-inch semiconductor wafer. The irradiation with the laser light was performed under the following conditions.
(A) Laser
Figure BDA0002453576670000461
(B) Lens for condensing light
Multiplying power of 50 times
NA 0.55
Transmittance at laser wavelength of 60%
(C) The moving speed of the mounting table on which the semiconductor substrate is mounted is 100 mm/sec
After forming the modified region in the semiconductor wafer, the protective tape for back grinding was bonded to the front surface of the semiconductor wafer, and the back surface was ground using a back grinder (trade name "DGP 8760", manufactured by DISCO inc.) so that the thickness of the semiconductor wafer became 30 μm.
The semiconductor wafer having the modified region formed thereon and the dicing ring were bonded to the dicing die-bonding films obtained in examples and comparative examples. Then, the semiconductor wafer and the die bond film were cut using a die separation apparatus (trade name "DDS 2300", manufactured by DISCO inc.). Specifically, first, the semiconductor wafer was cut by cold spreading using a cold spreading unit under conditions of a temperature of-15 ℃, a spreading rate of 100 mm/sec, and a spreading amount of 15 mm. After cold expansion, it was confirmed that there was no problem in the cleavage and the floating of the semiconductor chip with the die bond film.
After the semiconductor wafer and the die-bonding film were cut, the cold-expanding unit was used as it was to expand at room temperature under conditions of 0.3 mm/sec expansion rate and 8mm expansion amount at room temperature. Then, the area of the portion of the die-bonding film floating from the dicing tape (the ratio of the area of the semiconductor chip with the die-bonding film floating when the area of the entire die-bonding film was set to 100%) was observed with a microscope. The ratio of the area of the floating portion was evaluated as O when the ratio was less than 30%, as Δ when the ratio was 30 to 50%, and as X when the ratio was more than 50%.
[ Table 1]
Figure BDA0002453576670000471
[ Table 2]
Figure BDA0002453576670000481
To summarize the above, the configuration of the present invention and its modifications are attached below.
[1] A dicing die-bonding film comprising:
a dicing tape having a laminated structure including a substrate and an adhesive layer; and
an adhesive layer releasably adhered to the adhesive layer in the dicing tape,
in the pressure-sensitive adhesive layer, the surface of the pressure-sensitive adhesive layer on the side of adhesion has a water contact angle of 110 DEG or less and an arithmetic mean surface roughness Ra of 1.0 [ mu ] m or less.
[2] The dicing die-bonding film according to [1], wherein the water contact angle is 108 ° or less (preferably 105 ° or less).
[3] The dicing die-bonding film according to [1] or [2], wherein the water contact angle is 80 ° or more (preferably 84 ° or more, more preferably 88 ° or more).
[4] The dicing die-bonding film according to any one of [1] to [3], wherein the arithmetic average surface roughness Ra is 0.5 μm or less (preferably 0.3 μm or less).
[5] The dicing die-bonding film according to any one of [1] to [4], wherein the surface of the pressure-sensitive adhesive layer has a polar component value of surface free energy, which is obtained from Kaelble Uy's equation using a contact angle of water and a contact angle of diiodomethane, of 0.10 or more (preferably 0.20 or more, more preferably 0.40 or more).
[6] The dicing die-bonding film according to any one of [1] to [5], wherein the adhesive layer contains an acrylic polymer as a base polymer.
[7] The dicing die-bonding film according to [6], wherein the acrylic polymer contains a hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group as a monomer component.
[8] The dicing die-bonding film according to [7], wherein the total number of carbon atoms in the ester portion of the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group is 6 to 10.
[9] The dicing die-bonding film according to [6], wherein the total number of carbon atoms in the ester portion of the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group is 2 to 4.
[10] The dicing die-bonding film according to any one of [7] to [9], wherein the proportion of the hydrocarbon group-containing (meth) acrylate optionally having an alkoxy group in all monomer components for forming the acrylic polymer is 20 mol% or more (preferably 30 mol% or more, more preferably 40 mol% or more).
[11] The dicing die-bonding film according to any one of [6] to [10], wherein the acrylic polymer contains a hydroxyl group-containing monomer as a monomer component.
[12] The dicing die-bonding film according to [11], wherein the hydroxyl group-containing monomer is 2-hydroxyethyl (meth) acrylate.
[13] The dicing die-bonding film according to [11] or [12], wherein the proportion of the hydroxyl group-containing monomer in all monomer components for forming the acrylic polymer is 5 to 80 mol%.
[14] The dicing die-bonding film according to any one of [6] to [13], wherein the acrylic polymer contains a nitrogen atom-containing monomer (preferably a morpholine-containing monomer, more preferably (meth) acryloyl morpholine) as a monomer component.
[15] The dicing die-bonding film according to [14], wherein the proportion of the nitrogen atom-containing monomer in all monomer components for forming the acrylic polymer is 3 to 50 mol%.
[16] The dicing die-bonding film according to any one of [6] to [15], wherein the total ratio of the hydroxyl group-containing monomer and the nitrogen atom-containing monomer in all monomer components for forming the acrylic polymer is 10 to 60 mol%.
[17] The dicing die-bonding film according to any one of [6] to [16], wherein the acrylic polymer contains: a structural unit derived from a monomer having a 1 st functional group, and a structural unit derived from a compound having a 2 nd functional group and a radiation-polymerizable functional group that are reactive with the 1 st functional group.
[18] The dicing die-bonding film according to [17], wherein the combination of the 1 st functional group and the 2 nd functional group is a combination of a hydroxyl group and an isocyanate group, or a combination of an isocyanate group and a hydroxyl group.
[19] The dicing die-bonding film according to [17], wherein the 1 st functional group is a hydroxyl group and the 2 nd functional group is an isocyanate group.
[20] The dicing die-bonding film according to any one of [17] to [19], wherein the compound having the 2 nd functional group and the radiation-polymerizable functional group is a compound having a radiation-polymerizable carbon-carbon double bond (particularly a (meth) acryloyl group) and an isocyanate group.
[21] The dicing die-bonding film according to any one of [17] to [20], wherein the compound having the 2 nd functional group and the radiation polymerizable functional group is 2- (meth) acryloyloxyethyl isocyanate.
[22] The dicing die-bonding film according to any one of [17] to [21], wherein a molar ratio of the structural unit derived from the monomer having the 1 st functional group to the compound having the 2 nd functional group and the radiation-polymerizable functional group is 0.95 or more (preferably 1.00 or more, more preferably 1.05 or more, and further preferably 1.10 or more).
[23] The dicing die-bonding film according to any one of [17] to [22], wherein a molar ratio of the structural unit derived from the monomer having the 1 st functional group to the compound having the 2 nd functional group and the radiation-polymerizable functional group is 10.00 or less (preferably 5.00 or less, more preferably 3.00 or less, further preferably 2.00 or less, further preferably 1.50 or less, and particularly preferably 1.30 or less).
[24] The dicing die-bonding film according to any one of [1] to [23], wherein the pressure-sensitive adhesive layer contains a crosslinking agent (particularly a polyisocyanate compound).
[25] The dicing die-bonding film according to [24], wherein the amount of the crosslinking agent used is 0.1 to 5 parts by mass with respect to 100 parts by mass of the base polymer.
[26] The dicing die-bonding film according to any one of [1] to [25], wherein the adhesive layer is a curing catalyst (particularly dibutyltin dilaurate).

Claims (4)

1. A dicing die-bonding film comprising:
a dicing tape having a laminated structure including a substrate and an adhesive layer; and
an adhesive layer releasably adhered to the adhesive layer in the dicing tape,
in the pressure-sensitive adhesive layer, the surface of the pressure-sensitive adhesive layer on the side of adhesion has a water contact angle of 110 DEG or less and an arithmetic mean surface roughness Ra of 1.0 [ mu ] m or less.
2. The dicing die-bonding film according to claim 1, wherein the surface of the adhesive layer has a polar component value of surface free energy of 0.10 or more, which is obtained from the Kaelble Uy equation using a contact angle of water and a contact angle of diiodomethane.
3. The dicing die-bonding film according to claim 1 or 2, wherein the adhesive layer contains an acrylic polymer containing a hydrocarbon-based (meth) acrylate optionally having an alkoxy group, and a hydroxyl-containing monomer as monomer components.
4. The dicing die-bonding film according to claim 3, wherein the adhesive layer contains a polyisocyanate compound as a crosslinking agent.
CN202010299872.8A 2019-04-17 2020-04-16 Dicing die bonding film Withdrawn CN111826100A (en)

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TWI783530B (en) * 2021-06-18 2022-11-11 李志雄 Temporarily bonding laminated body and application of wafer thinning preparation method
KR20230025233A (en) * 2021-08-13 2023-02-21 주식회사 제우스 Wafer processing method

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CN108728000A (en) * 2017-04-17 2018-11-02 日东电工株式会社 Cut die bonding film
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