CN114730707A - Sheet for manufacturing semiconductor device and method for manufacturing semiconductor chip with film-like adhesive - Google Patents

Sheet for manufacturing semiconductor device and method for manufacturing semiconductor chip with film-like adhesive Download PDF

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Publication number
CN114730707A
CN114730707A CN202180006203.XA CN202180006203A CN114730707A CN 114730707 A CN114730707 A CN 114730707A CN 202180006203 A CN202180006203 A CN 202180006203A CN 114730707 A CN114730707 A CN 114730707A
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China
Prior art keywords
adhesive
film
intermediate layer
mass
semiconductor device
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CN202180006203.XA
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Chinese (zh)
Inventor
岩屋涉
佐藤阳辅
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Lintec Corp
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Lintec Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/14—Semiconductor wafers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68354—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used to support diced chips prior to mounting

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a semiconductor device manufacturing sheet (101) comprising a base material (11), an adhesive layer (12), an intermediate layer (13), and a film-like adhesive (14), wherein the semiconductor device manufacturing sheet (101) is configured by laminating the adhesive layer (12), the intermediate layer (13), and the film-like adhesive (14) in this order on the base material (11), the film-like adhesive (14) contains an antistatic agent, the content of the antistatic agent is 3 mass% or less with respect to the total mass of the film-like adhesive (14), the intermediate layer (13) contains a non-silicon resin having a weight-average molecular weight of 100000 or less as a main component, and the surface resistivity of the surface of the film-like adhesive (14) on the side of the intermediate layer (13) is 1 x 1013Omega is less than or equal to.

Description

Sheet for manufacturing semiconductor device and method for manufacturing semiconductor chip with film-like adhesive
Technical Field
The present invention relates to a sheet for manufacturing a semiconductor device and a method for manufacturing a semiconductor chip with a film-like adhesive.
The present application claims priority based on Japanese patent application No. 2020 and 058734 filed in Japan on 27.3.2020, and the contents thereof are incorporated herein.
Background
In the manufacture of a semiconductor device, a semiconductor chip with a film-like adhesive is used, which includes a semiconductor chip and a film-like adhesive provided on the back surface of the semiconductor chip.
As an example of a method for manufacturing a semiconductor chip with a film-like adhesive, the following manufacturing method can be mentioned.
First, a dicing die is attached to the back surface of a semiconductor wafer.
As the dicing solid-state wafer, for example, a dicing solid-state wafer including a support sheet and a film-like adhesive provided on a surface of the support sheet is exemplified. The support sheet may serve as a cutting sheet. As the support sheet, for example, there are several support sheets having different constitutions as follows: a support sheet including a base material and an adhesive layer provided on one surface of the base material; a support sheet composed only of a base material, and the like. The support sheet provided with the adhesive layer has a film-like adhesive provided on the outermost surface on the adhesive layer side. The dicing die is attached to the back surface of the semiconductor wafer with the film-like adhesive interposed therebetween.
Then, the semiconductor wafer on the support sheet is cut off simultaneously with the film-like adhesive by blade dicing. The "dicing" of the semiconductor wafer is also referred to as "dicing", whereby the semiconductor wafer is singulated into target semiconductor chips. The film-like adhesive is cut along the outer periphery of the semiconductor chip. Thus, a semiconductor chip with a film-like pressure-sensitive adhesive, which includes a semiconductor chip and a film-like pressure-sensitive adhesive provided on the back surface of the semiconductor chip after cutting, can be obtained, and a semiconductor chip group with a film-like pressure-sensitive adhesive, in which a plurality of the semiconductor chips with a film-like pressure-sensitive adhesive are held in an aligned state on a support sheet, can be obtained.
Then, the semiconductor chip with the film-like adhesive is pulled away from the support sheet to be picked up. When a support sheet having a curable adhesive layer is used, the adhesive layer is cured to reduce the adhesiveness, and thus the sheet can be easily picked up.
From the above, a semiconductor chip with a film-like adhesive for manufacturing a semiconductor device can be obtained.
As another example of the method for manufacturing a semiconductor chip with a film-like adhesive, the following manufacturing method can be mentioned.
First, a back-grinding tape (also referred to as a "surface-protecting tape") is attached to a circuit-formed surface of a semiconductor wafer.
Then, a pre-divided region is set in the semiconductor wafer, and a laser beam is irradiated so as to focus the region included in the pre-divided region on the focal point, thereby forming a modified layer in the semiconductor wafer. Then, the back surface of the semiconductor wafer is ground using a grinder, whereby the thickness of the semiconductor wafer is adjusted to a target value. By using the force applied to the semiconductor wafer during polishing at this time, the semiconductor wafer is divided (singulated) at the portion where the modified layer is formed, thereby producing a plurality of semiconductor chips. Such a method of dividing a semiconductor wafer with formation of a modified layer is called stealth dicing (registered trademark), and is fundamentally completely different from laser dicing in which a semiconductor wafer is irradiated with laser light to cut the semiconductor wafer at the irradiated portion and cut the semiconductor wafer from the surface thereof.
Then, a single fixed wafer is attached to the surface of all of the semiconductor chips fixed to the back-grinding tape, which has been ground as described above (in other words, the ground surface). The fixed wafer may be the same as the above-described diced fixed wafer. As described above, the die is not used only when the semiconductor wafer is diced, and the die can be designed to have the same configuration as that of the diced die in some cases. The die is attached to the back surface of the semiconductor chip with the film-like adhesive therein.
Then, after the back grinding tape is removed from the semiconductor chip, the fixed wafer is stretched in a direction parallel to the surface thereof (for example, the surface to which the film-like adhesive is attached to the semiconductor chip), that is, in a so-called spreading (cold spreading), while being cooled, thereby cutting the film-like adhesive along the outer periphery of the semiconductor chip.
As a result, a semiconductor chip with a film-like adhesive can be obtained, which includes a semiconductor chip and a cut film-like adhesive provided on the back surface of the semiconductor chip.
Then, as in the case of dicing with the blade described above, the semiconductor chip with the film-like adhesive is picked up by pulling it off from the support sheet, thereby obtaining a semiconductor chip with a film-like adhesive for use in manufacturing a semiconductor device.
Both the dicing die and the die bonding sheet can be used for manufacturing a semiconductor chip with a film-like adhesive, and the target semiconductor device can be finally manufactured. In the present specification, the diced solid-state wafer and the solid-state wafer are collectively referred to as a "semiconductor device manufacturing wafer".
As a sheet for manufacturing a semiconductor device, for example, a dicing die-bonding tape (corresponding to the dicing die-bonding sheet) having a structure in which a base layer (corresponding to the support sheet) and an adhesive layer (corresponding to the film-like adhesive) are laminated in direct contact with each other is disclosed (see patent document 1). In the dicing die-bonding tape, the 90-degree peel force at-15 ℃ of the base layer and the pressure-sensitive adhesive layer is adjusted to be within a specific range, and therefore the pressure-sensitive adhesive layer can be cut with high precision by spreading. Further, since the 90-degree peel force at 23 ℃ of the base material layer and the adhesive layer is adjusted to be within a specific range, when the dicing die-bonding tape is used, the semiconductor chip with the adhesive layer (corresponding to the semiconductor chip with the film-like adhesive) can be easily picked up, and the semiconductor wafer and the semiconductor chip can be suppressed from being peeled from the adhesive layer until the picking up.
On the other hand, the picked-up semiconductor chip is die-bonded to a circuit surface of a substrate having a circuit with, for example, a film-like adhesive, and after wire bonding, the entire semiconductor chip is sealed with a resin.
Using the semiconductor package obtained in the above manner, a target semiconductor device can be finally manufactured.
Patent document 2 discloses a film for a semiconductor device (corresponding to the dicing die) in which an adhesive film with a dicing sheet is laminated on a cover film at predetermined intervals. It is described that an antistatic agent or a conductive substance may be added to a base material, an adhesive layer, or an adhesive film in order to prevent generation of static electricity and damage to a circuit due to electrification of a semiconductor wafer or the like caused by generation of static electricity.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2018-56289
Patent document 2: japanese laid-open patent publication No. 2012-59768
Disclosure of Invention
Technical problem to be solved by the invention
However, the dicing die bond tape disclosed in patent document 1 is suitable for stealth dicing (registered trademark), but is not suitable for blade dicing. When the dicing tape is used for dicing, Whisker-like cutting chips (sometimes referred to as "whiskers (Whisker)" in the art) are likely to be generated on the base material layer, and the dicing suitability for dividing a semiconductor wafer is poor.
Further, if an antistatic agent is used in the film-like adhesive in order to prevent the generation of static electricity, the reliability of a semiconductor package obtained using the film-like adhesive may be impaired.
The purpose of the present invention is to provide a sheet for manufacturing a semiconductor device, which has excellent suitability for dividing a semiconductor wafer, contains an antistatic agent in a film-like adhesive, and has excellent reliability of a semiconductor package obtained using the film-like adhesive, and a method for manufacturing a semiconductor chip with a film-like adhesive using the sheet for manufacturing a semiconductor device.
Means for solving the problems
The present invention has the following aspects.
[1] A sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
[2] The sheet for manufacturing a semiconductor device according to [1], wherein a ratio of a concentration of silicon to a total concentration of carbon, oxygen, nitrogen and silicon is 1 to 20% when a surface of the intermediate layer on the film-like binder side is analyzed by X-ray photoelectron spectroscopy.
[3] The sheet for manufacturing a semiconductor device according to [1] or [2], wherein the intermediate layer contains an ethylene-vinyl acetate copolymer or a polyolefin as the non-silicon resin.
[4] The sheet for manufacturing a semiconductor device according to [3], wherein,
the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin,
in the ethylene-vinyl acetate copolymer, the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 10 to 40% by mass.
[5] The sheet for manufacturing a semiconductor device according to [4], wherein,
the intermediate layer contains an ethylene-vinyl acetate copolymer and a silicone compound as the non-silicone resin,
in the intermediate layer, the content of the ethylene-vinyl acetate copolymer is 90-99.99% by mass relative to the total mass of the intermediate layer,
in the intermediate layer, the content of the siloxane compound is 0.01-10% by mass relative to the total mass of the intermediate layer.
[6] A method for manufacturing a semiconductor chip with a film-like adhesive, comprising:
a step of attaching the back surface of a semiconductor wafer to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet according to any one of [1] to [5] to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive and the semiconductor wafer are laminated in this order;
cutting the film-like adhesive while the semiconductor wafer is being diced to obtain semiconductor chips with the film-like adhesive; and
and a step of pulling the semiconductor chip with the film-like adhesive off the base material, the adhesive layer, and the intermediate layer to pick up the semiconductor chip.
[7] A method for manufacturing a semiconductor chip with a film-like adhesive, comprising:
a step of attaching the back surfaces of the semiconductor chip groups in which the plurality of semiconductor chips are aligned to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet according to any one of [1] to [5] to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive, and the semiconductor chip groups are stacked in this order;
cutting the film-like adhesive to obtain a semiconductor chip with the film-like adhesive; and
and a step of pulling the semiconductor chip with the film-like adhesive off the base material, the adhesive layer, and the intermediate layer to pick up the semiconductor chip.
Effects of the invention
According to the present invention, a semiconductor device-manufacturing sheet having excellent suitability for dividing a semiconductor wafer, an antistatic agent contained in a film-like adhesive, and excellent reliability of packaging, and a method for manufacturing a semiconductor chip with a film-like adhesive using the semiconductor device-manufacturing sheet can be provided.
Drawings
Fig. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention.
Fig. 2 is a plan view of the semiconductor device manufacturing sheet shown in fig. 1.
Fig. 3A is a sectional view for schematically illustrating one example of a method for using a semiconductor device-manufacturing sheet according to one embodiment of the present invention.
Fig. 3B is a sectional view for schematically illustrating one example of a method of using a semiconductor device-manufacturing sheet according to one embodiment of the present invention.
Fig. 3C is a sectional view for schematically illustrating one example of a method for using a semiconductor device-manufacturing sheet according to one embodiment of the present invention.
Fig. 4A is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.
Fig. 4B is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.
Fig. 4C is a sectional view for schematically illustrating one example of a manufacturing method of a semiconductor chip.
Fig. 5A is a sectional view for schematically illustrating another example of a method for using a semiconductor device-manufacturing sheet according to an embodiment of the present invention.
Fig. 5B is a sectional view for schematically illustrating another example of a method of using a sheet for manufacturing a semiconductor device according to an embodiment of the present invention.
Fig. 5C is a sectional view for schematically illustrating another example of a method for using a semiconductor device-manufacturing sheet according to an embodiment of the present invention.
Detailed Description
Wafer for manufacturing semiconductor device
A sheet for manufacturing a semiconductor device according to one embodiment of the present invention includes a substrate, an adhesive layer, an intermediate layer, and a film-like adhesive, and the sheet for manufacturing a semiconductor device is obtained by sequentially laminating the adhesive layer, the intermediate layer, and the film on the substrateA film-like pressure-sensitive adhesive containing an antistatic agent in an amount of 3 mass% or less based on the total mass of the film-like pressure-sensitive adhesive, the intermediate layer containing a non-silicone resin having a weight-average molecular weight of 100000 or less as a main component, and the surface resistivity of the surface of the film-like pressure-sensitive adhesive on the side of the intermediate layer being 1 × 1013Omega is less than or equal to.
When the semiconductor device-manufacturing sheet of the present embodiment is used as a dicing solid wafer to perform dicing with a blade, the semiconductor device-manufacturing sheet is provided with the intermediate layer, whereby the blade can be easily prevented from reaching the base material or the adhesive layer, and generation of Whisker-like cutting chips (also called whiskers (hereinafter, not limited to cutting chips from the base material or the adhesive layer, and sometimes simply referred to as "cutting chips") from the base material or the adhesive layer can be suppressed. In addition, the cutting chips from the intermediate layer can be suppressed from being generated by making the main component of the intermediate layer cut by the blade be a non-silicone resin having a weight average molecular weight of 100000 or less, particularly 100000 or less.
On the other hand, when the semiconductor device manufacturing sheet of the present embodiment is used as a die bonding sheet and dicing (stealth dicing (registered trademark)) accompanied by formation of a modified layer in a semiconductor wafer is performed, the film-like adhesive can be cut at a target site with high precision and cutting defects can be suppressed by providing the semiconductor device manufacturing sheet with the intermediate layer and then stretching, that is, spreading, the semiconductor device manufacturing sheet in a direction parallel to the surface thereof (for example, the surface to which the film-like adhesive is attached to the semiconductor chip). This is considered to be because the provision of the intermediate layer enables the extended stress to be efficiently utilized for the inter-chip distance expansion.
As a result, the semiconductor device manufacturing sheet according to the present embodiment can suppress the generation of chips from the base material and the intermediate layer when blade dicing is performed, can suppress the cutting failure of the film-like adhesive when spreading, has a characteristic of suppressing the occurrence of failure when dividing a semiconductor wafer, and has excellent suitability for dividing a semiconductor wafer.
In the semiconductor device manufacturing sheet of the present embodiment, the film-like pressure-sensitive adhesive contains an antistatic agent, and the surface resistivity of the surface on the middle layer side of the film-like pressure-sensitive adhesive can be set to 1 × 1013Omega or less, can prevent generating static electricity and damaging the circuit due to the static electricity generated to charge the semiconductor wafer. In addition, in the sheet for manufacturing a semiconductor device according to the present embodiment, by setting the content of the antistatic agent to 3 mass% or less with respect to the total mass of the film-like adhesive, the reliability of the semiconductor package obtained using the film-like adhesive, particularly the reliability of the semiconductor package of a chip/chip type in which semiconductor chips are further stacked on semiconductor chips, is excellent.
The surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less, preferably 5X 1011Omega is 1 × 10 or more13Omega or less, more preferably 1X 1012Omega is more than or equal to 8 multiplied by 1012Omega is less than or equal to.
Examples of the antistatic agent contained in the film-like binder include carbon materials, ionic materials, metal fine particles, metal oxides, metal fillers, and surfactants.
From the viewpoint of further exhibiting the effects of the present embodiment, the antistatic agent preferably contains at least one selected from the group consisting of a carbon material and an ionic material.
Examples of the carbon material include carbon nanotubes, carbon nanofibers, graphene, carbon black, milled carbon fibers (milled carbon fibers), and graphite. These materials may be commercially available products.
These carbon materials may be used singly or in combination of two or more.
The carbon material is preferably at least one selected from the group consisting of carbon nanotubes, graphene, and carbon black.
The ionic material is preferably at least one selected from the group consisting of ionic liquids and ionic polymers.
The content of the antistatic agent may be 3 mass% or less, 0.1 mass% or more and 3.0 mass% or less, 0.2 mass% or more and 3.0 mass% or less, 0.3 mass% or more and 3.0 mass% or less, 0.4 mass% or more and 3.0 mass% or less, and 0.5 mass% or more and 2.9 mass% or less with respect to the total mass of the film-shaped adhesive.
In the present specification, unless otherwise specified, "weight average molecular weight" is a polystyrene equivalent value measured by a Gel Permeation Chromatography (GPC) method.
The method of using the semiconductor device manufacturing sheet according to this embodiment will be described in detail later.
Hereinafter, the semiconductor device manufacturing sheet according to the present embodiment will be described in detail with reference to the drawings. In addition, for the sake of easy understanding of the features of the present invention, the drawings used in the following description may be enlarged to show the main portions, and the dimensional ratios of the respective components are not necessarily the same as the actual ones.
Fig. 1 is a cross-sectional view schematically showing a semiconductor device manufacturing sheet according to an embodiment of the present invention, and fig. 2 is a plan view of the semiconductor device manufacturing sheet shown in fig. 1.
In the drawings subsequent to fig. 2, the same components as those shown in the already described drawings are denoted by the same reference numerals as in the already described drawings, and detailed description thereof will be omitted.
The semiconductor device manufacturing sheet 101 shown here includes a substrate 11, and is configured by laminating an adhesive layer 12, an intermediate layer 13, and a film-like adhesive 14 on the substrate 11 in this order. The semiconductor device manufacturing sheet 101 further includes a release film 15 on a surface (hereinafter, sometimes referred to as "first surface") 14a of the film-like adhesive 14 opposite to the side on which the intermediate layer 13 is provided.
In the semiconductor device manufacturing sheet 101, an adhesive layer 12 is provided on one surface (in this specification, may be referred to as a "first surface") 11a of a base material 11. An intermediate layer 13 is provided on a surface (in this specification, sometimes referred to as a "first surface") 12a of the adhesive layer 12 opposite to the side on which the substrate 11 is provided. A film-like adhesive 14 is provided on a surface (in this specification, sometimes referred to as a "first surface") 13a of the intermediate layer 13 opposite to the side on which the adhesive layer 12 is provided. A release film 15 is provided on the first surface 14a of the film-like adhesive 14. Thus, the semiconductor device manufacturing sheet 101 is formed by sequentially laminating the substrate 11, the adhesive layer 12, the intermediate layer 13, and the film-like adhesive 14 in the thickness direction thereof.
The semiconductor device manufacturing sheet 101 is used by attaching the first surface 14a of the film-like adhesive 14 to the back surface of a semiconductor wafer, a semiconductor chip, or a semiconductor wafer (not shown) which is not completely divided, with the release film 15 removed.
In this specification, the surface of the semiconductor wafer or the semiconductor chip on which the circuit is formed is referred to as a "circuit forming surface", and the surface opposite to the circuit forming surface is referred to as a "back surface".
In the present specification, a laminate having a structure in which a base material and an adhesive agent layer are sequentially laminated in the thickness direction thereof and an intermediate layer is not laminated may be referred to as a "support sheet". In fig. 1, reference numeral 1 denotes a support sheet.
A laminate having a structure in which a substrate, an adhesive layer, and an intermediate layer are laminated in this order in the thickness direction thereof is sometimes referred to as a "laminate sheet". In fig. 1, reference numeral 10 denotes a laminate sheet. The laminate of the support sheet and the intermediate layer is contained in the laminate sheet.
When the intermediate layer 13 and the film-like adhesive 14 are viewed from above the intermediate layer 13 and the film-like adhesive 14 in a plan view, the planar shapes of the intermediate layer 13 and the film-like adhesive 14 are both circular, and the diameter of the intermediate layer 13 is the same as the diameter of the film-like adhesive 14.
In the semiconductor device manufacturing sheet 101, the intermediate layer 13 and the film-like adhesive 14 are disposed so that the centers of the intermediate layer 13 and the film-like adhesive 14 are aligned, in other words, the intermediate layer 13 and the film-like adhesive 14 are disposed so that the outer peripheries of the intermediate layer 13 and the film-like adhesive 14 are aligned in the radial direction.
The areas of the first surface 13a of the intermediate layer 13 and the first surface 14a of the film-like adhesive 14 are smaller than those of the first surface 14a of the adhesive layer 12One face 12 a. And the width W of the intermediate layer 1313Maximum value (i.e., diameter) of (c) and width W of the film-like adhesive 1414Are smaller than the maximum of the width of the adhesive layer 12 and the maximum of the width of the substrate 11. Therefore, in the semiconductor device manufacturing sheet 101, a part of the first surface 12a of the adhesive layer 12 is not covered with the intermediate layer 13 and the film-like adhesive 14. In the first surface 12a of the adhesive layer 12, a region where the intermediate layer 13 and the film-like adhesive 14 are not laminated is directly in contact with the release film 15 and laminated, and the region is exposed in a state where the release film 15 is removed (hereinafter, this region may be referred to as a "non-laminated region" in the present specification).
As described above, in the semiconductor device manufacturing sheet 101 including the release film 15, the region of the adhesive layer 12 not covered with the intermediate layer 13 and the film-like adhesive 14 may or may not have a region where the release film 15 is not laminated.
The semiconductor device manufacturing sheet 101 in a state where the film-like adhesive 14 is not cut and is attached to the semiconductor wafer, the semiconductor chip, or the like by the film-like adhesive 14 can be fixed by attaching a part of the non-lamination region of the adhesive layer 12 to a jig such as a ring frame for fixing the semiconductor wafer. Therefore, it is not necessary to separately provide a jig adhesive layer for fixing the semiconductor device manufacturing sheet 101 to the jig on the semiconductor device manufacturing sheet 101. Further, since the adhesive layer for a jig is not required to be provided, the sheet 101 for manufacturing a semiconductor device can be manufactured inexpensively and efficiently.
Thus, the semiconductor device manufacturing sheet 101 has an excellent effect by not having a jig adhesive layer, but may have a jig adhesive layer. In this case, the adhesive layer for a jig is provided in a region near the peripheral portion on the surface of any one of the layers constituting the semiconductor device manufacturing sheet 101. Such a region includes the non-laminated region on the first surface 12a of the adhesive layer 12.
The pressure-sensitive adhesive layer for a jig may be a known pressure-sensitive adhesive layer, and may have, for example, a single-layer structure containing a pressure-sensitive adhesive component, or a multilayer structure in which layers containing a pressure-sensitive adhesive component are laminated on both surfaces of a sheet as a core material.
As will be described later, when the semiconductor device manufacturing sheet 101 is stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the adhesive agent layer 12) to perform so-called spreading, the semiconductor device manufacturing sheet 101 can be easily spread by making the non-laminated region present on the first surface 12a of the adhesive agent layer 12. Further, not only the film-shaped adhesive 14 can be easily cut, but also the peeling of the intermediate layer 13 and the film-shaped adhesive 14 from the adhesive layer 12 can be suppressed.
In the semiconductor device-manufacturing sheet 101, the intermediate layer 13 contains a non-silicon resin having a weight-average molecular weight of 100000 or less as a main component.
The semiconductor device manufacturing sheet according to the present embodiment is not limited to the semiconductor device manufacturing sheet shown in fig. 1 and 2, and a part of the structure of the semiconductor device manufacturing sheet shown in fig. 1 and 2 may be modified, deleted, or added within a range not to impair the effect of the present invention.
For example, the semiconductor device-manufacturing sheet of the present embodiment may include another layer not belonging to any of the substrate, the adhesive layer, the intermediate layer, the film-like adhesive, the release film, and the jig adhesive layer. As shown in fig. 1, the semiconductor device-manufacturing sheet of the present embodiment preferably includes an adhesive layer in direct contact with a substrate, an intermediate layer in direct contact with the adhesive layer, and a film-like adhesive in direct contact with the intermediate layer.
For example, in the semiconductor device manufacturing sheet of the present embodiment, the planar shapes of the intermediate layer and the film-like adhesive may be shapes other than circular, and the planar shapes of the intermediate layer and the film-like adhesive may be the same as or different from each other. Further, it is preferable that the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are both smaller than the area of the surface of the layer closer to the substrate than the first surface of the intermediate layer (for example, the first surface of the adhesive layer), and the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive may be the same as or different from each other. The outer circumferential positions of the intermediate layer and the film-like adhesive may be uniform or nonuniform in the radial direction.
Next, the layers constituting the semiconductor device manufacturing sheet of this embodiment will be described in more detail.
O base material
The substrate is in the shape of a sheet or a film.
The material constituting the base material is preferably a variety of resins, and specific examples thereof include polyethylene (low density polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene (PP), polybutene, polybutadiene, polymethylpentene, styrene-ethylene-butene-styrene block copolymer, polyvinyl chloride, vinyl chloride copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyurethane, urethane acrylate, Polyimide (PI), ionomer resin, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ethylene copolymer other than ethylene- (meth) acrylic acid copolymer and ethylene- (meth) acrylate copolymer, polystyrene, polyethylene terephthalate, and polyethylene terephthalate, and polyethylene terephthalate, and polyethylene terephthalate, and polyethylene terephthalate, polyethylene terephthalate, Polycarbonate, fluororesin, hydrogenated product, modified product, crosslinked product, copolymer of any of the above resins, and the like.
In the present specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". Similar terms to (meth) acrylic acid are also the same, and for example, "(meth) acrylate" is a concept including both "acrylate" and "methacrylate", and "(meth) acryl" is a concept including both "acryl" and "methacryl".
The resin constituting the base material may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
The substrate may be composed of one layer (single layer) or a plurality of layers of two or more layers, and when the substrate is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effect of the present invention is not impaired.
In the present specification, the phrase "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers may be different from each other, or only a part of layers may be the same" and "a plurality of layers may be different from each other" means "at least one of the constituent material and the thickness of each layer is different from each other".
The thickness of the substrate may be appropriately selected according to the purpose, but is preferably 50 to 300. mu.m, and more preferably 60 to 150. mu.m. By setting the thickness of the base material to the lower limit or more, the structure of the base material is further stabilized. By setting the thickness of the base material to the upper limit or less, the film-like adhesive can be cut more easily during dicing and during the expansion of the semiconductor device manufacturing sheet.
The "thickness of the substrate" refers to the thickness of the entire substrate, and for example, the thickness of the substrate composed of a plurality of layers refers to the total thickness of all the layers constituting the substrate.
In the present specification, unless otherwise specified, "thickness" is a value represented by an average of thicknesses measured at randomly selected 5 points, and can be obtained using a constant-pressure thickness gauge in accordance with JIS K7130.
In order to improve the adhesion between the substrate and another layer such as an adhesive layer provided on the substrate, the surface of the substrate may be subjected to an embossing treatment such as a sandblasting treatment, a solvent treatment, or an embossing (emboss) treatment; oxidation treatment by corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone-ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, and the like.
The surface of the substrate may be subjected to a primer treatment.
The substrate may further have: an antistatic coating; a layer for preventing the adhesion of the base material to another sheet or the adhesion of the base material to a suction table (suction table) when the base material is stacked on a die bonding sheet for storage.
The base material may contain known various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin.
The optical properties of the base material are not particularly limited as long as the effects of the present invention are not impaired. The substrate can be, for example, transmissive to laser light or energy radiation.
The substrate can be produced by a known method. For example, a base material containing a resin (resin as a constituent material) can be produced by molding the resin or a resin composition containing the resin.
Adhesive layer
The adhesive layer is in a sheet or film shape and contains an adhesive.
The adhesive layer can be formed using an adhesive composition containing the adhesive. For example, an adhesive agent layer can be formed at a target site by applying an adhesive agent composition to a surface to be formed of the adhesive agent layer and drying the composition as necessary.
In the adhesive agent layer, the ratio of the total content of one or two or more of the below-described components contained in the adhesive agent layer to the total mass of the adhesive agent layer is not more than 100 mass%.
Similarly, in the adhesive composition, the ratio of the total content of one or two or more of the components contained in the adhesive composition, which will be described later, to the total mass of the adhesive composition is not more than 100% by mass.
The adhesive composition may be applied by a known method, and examples thereof include a method using various coating machines such as an air knife coater, a blade coater, a bar coater, a gravure coater, a roll coater, a curtain coater, a die coater, a knife coater, a screen coater, a meyer bar coater, and a kiss coater.
The drying conditions of the adhesive composition are not particularly limited, and when the adhesive composition contains a solvent described later, it is preferably dried by heating, and in this case, it is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
Examples of the adhesive include adhesive resins such as acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins, and acrylic resins are preferred.
In the present specification, the "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, the adhesive resin includes not only a resin having adhesiveness of the resin itself but also a resin exhibiting adhesiveness by being used together with other components such as an additive, a resin exhibiting adhesiveness due to the presence of an inducer such as heat or water, and the like.
The adhesive layer may be either curable or non-curable, and may be either energy ray-curable or non-energy ray-curable, for example. The physical properties of the curable adhesive layer before and after curing can be easily adjusted.
In the present specification, "energy ray" refers to a ray having an energy quantum in an electromagnetic wave or a charged particle beam. Examples of the energy ray include ultraviolet rays, radiation, and electron beams. For example, the ultraviolet rays can be irradiated by using a high-pressure mercury lamp, a fusion lamp (fusion lamp), a xenon lamp, a black light lamp, an LED lamp, or the like as an ultraviolet ray source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.
In the present specification, "energy ray-curable property" refers to a property of curing by irradiation with an energy ray, and "non-energy ray-curable property" refers to a property of not curing even by irradiation with an energy ray.
The adhesive layer may be composed of one layer (single layer) or a plurality of layers of two or more layers, and in the case of being composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
The thickness of the adhesive layer is preferably 1 to 100 μm, more preferably 1 to 60 μm, and particularly preferably 1 to 30 μm.
The "thickness of the adhesive agent layer" refers to the thickness of the entire adhesive agent layer, and for example, the thickness of the adhesive agent layer composed of a plurality of layers refers to the total thickness of all the layers constituting the adhesive agent layer.
The optical characteristics of the adhesive layer are not particularly limited as long as the effects of the present invention are not impaired. For example, the adhesive layer can transmit energy rays.
Next, the adhesive composition will be described.
The adhesive composition described below may contain one or more of the following components, for example, so that the total content (mass%) is not more than 100 mass%.
Adhesive composition
When the adhesive layer is energy ray-curable, examples of the adhesive composition containing an energy ray-curable adhesive, i.e., the energy ray-curable adhesive composition, include an adhesive composition (I-1) containing a non-energy ray-curable adhesive resin (I-1a) (hereinafter, sometimes abbreviated as "adhesive resin (I-1 a)") and an energy ray-curable compound; an adhesive composition (I-2) comprising an energy ray-curable adhesive resin (I-2a) (hereinafter, sometimes abbreviated as "adhesive resin (I-2 a)") wherein an unsaturated group is introduced into a side chain of the non-energy ray-curable adhesive resin (I-1 a); and an adhesive composition (I-3) containing the adhesive resin (I-2a) and an energy ray-curable compound.
< adhesive composition (I-1) >)
As described above, the adhesive composition (I-1) contains the non-energy ray-curable adhesive resin (I-1a) and the energy ray-curable compound.
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
The acrylic resin may have only one kind of structural unit, or two or more kinds of structural units, and when two or more kinds of structural units are used, the combination and ratio thereof may be arbitrarily selected.
The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-1).
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray.
Examples of the monomer in the energy ray-curable compound include polyvalent (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1, 4-butanediol di (meth) acrylate, and 1, 6-hexanediol (meth) acrylate; urethane (meth) acrylate; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates, and the like.
Examples of the oligomer in the energy ray-curable compound include oligomers obtained by polymerizing the above-mentioned monomers.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate oligomer in view of a large molecular weight and difficulty in lowering the elastic modulus of the adhesive agent layer.
The energy ray-curable compound contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-1), the content of the energy ray-curable compound is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition (I-1).
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the adhesive composition (I-1) preferably further contains a crosslinking agent.
The crosslinking agent reacts with the functional groups, for example, to crosslink the adhesive resins (I-1a) with each other. Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having an isocyanate group) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; epoxy crosslinking agents (crosslinking agents having a glycidyl group) such as ethylene glycol glycidyl ether; aziridine crosslinking agents (crosslinking agents having an aziridinyl group), such as hexa [1- (2-methyl) -aziridinyl ] triphosphizine; metal chelate crosslinking agents (crosslinking agents having a metal chelate structure) such as aluminum chelate; an isocyanurate-based crosslinking agent (a crosslinking agent having an isocyanurate skeleton), and the like.
The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of improving the cohesive force of the adhesive agent, improving the adhesive force of the adhesive agent layer, and facilitating the availability.
The crosslinking agent contained in the adhesive composition (I-1) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-1) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-1 a).
[ photopolymerization initiator ]
The adhesive composition (I-1) may further contain a photopolymerization initiator. The adhesive composition (I-1) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with a relatively low energy ray such as ultraviolet ray.
Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzylphenylsulfide and tetramethylthiuram monosulfide; α -ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil; dibenzoyl; a benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; 2-chloroanthraquinone, and the like.
Examples of the photopolymerization initiator include quinone compounds such as 1-chloroanthraquinone, and photosensitizers such as amines.
The pressure-sensitive adhesive composition (I-1) may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators, and when the number of photopolymerization initiators is two or more, the combination and ratio thereof may be arbitrarily selected.
When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-1) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the energy ray-curable compound.
[ other additives ]
The adhesive composition (I-1) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.
Examples of the other additives include known additives such as antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments and dyes), sensitizers, tackifiers, reaction retarders, and crosslinking accelerators (catalysts).
The reaction retarder is a component for suppressing the occurrence of an unintended crosslinking reaction in the adhesive composition (I-1) during storage, for example, due to the action of a catalyst mixed in the adhesive composition (I-1). Examples of the reaction retarder include a reaction retarder that forms a chelate complex by a chelating agent for a catalyst, and more specifically, a reaction retarder having two or more carbonyl groups (-C (═ O) -) in one molecule.
The adhesive composition (I-1) may contain only one other additive, or may contain two or more additives, and when two or more additives are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected depending on the kind thereof.
[ solvent ]
The adhesive composition (I-1) may contain a solvent. By containing the solvent, the applicability of the adhesive composition (I-1) to the surface to be coated is improved.
The solvent is preferably an organic solvent.
< adhesive composition (I-2) >)
As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a) in which an unsaturated group is introduced into the side chain of the non-energy ray-curable adhesive resin (I-1 a).
[ adhesive resin (I-2a) ]
The adhesive resin (I-2a) can be obtained, for example, by reacting an unsaturated group-containing compound having an energy ray-polymerizable unsaturated group with a functional group in the adhesive resin (I-1 a).
The unsaturated group-containing compound is a compound having a group capable of bonding to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the energy ray-polymerizable unsaturated group.
Examples of the energy ray-polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group (ethylene group), and an allyl group (2-propenyl group), and a (meth) acryloyl group is preferable.
Examples of the group capable of bonding to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group capable of bonding to a hydroxyl group or an amino group, and a hydroxyl group and an amino group capable of bonding to a carboxyl group or an epoxy group.
Examples of the unsaturated group-containing compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 10 to 90% by mass, based on the total mass of the adhesive composition (I-2).
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer, which is, for example, the same as the polymer in the adhesive resin (I-1a), is used as the adhesive resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.
The crosslinking agent in the adhesive composition (I-2) may be the same crosslinking agent as that in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-2) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When a crosslinking agent is used, the content of the crosslinking agent in the adhesive composition (I-2) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.3 to 15 parts by mass, based on 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation such as ultraviolet light.
The photopolymerization initiator in the adhesive composition (I-2) may be the same photopolymerization initiator as that in the adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-2) may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators, and when the number of photopolymerization initiators is two or more, the combination and ratio thereof may be arbitrarily selected.
When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-2) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ other additives and solvents ]
The adhesive composition (I-2) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.
Further, the adhesive composition (I-2) may also contain a solvent for the same purpose as in the adhesive composition (I-1).
Examples of the other additives and solvents in the adhesive composition (I-2) include the same additives and solvents as those in the adhesive composition (I-1).
The other additives and solvents contained in the adhesive composition (I-2) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The content of other additives and solvents in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected depending on the type thereof.
< adhesive composition (I-3) >)
As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound.
In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-3).
[ energy ray-curable Compound ]
Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers having an energy ray-polymerizable unsaturated group and curable by irradiation with an energy ray, and examples of the energy ray-curable compound include the same compounds as those contained in the adhesive composition (I-1).
The energy ray-curable compound contained in the adhesive composition (I-3) may be one kind only, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the energy ray-curable compound in the adhesive composition (I-3) is preferably 0.01 to 300 parts by mass, more preferably 0.03 to 200 parts by mass, and particularly preferably 0.05 to 100 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-2 a).
[ photopolymerization initiator ]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator can sufficiently undergo a curing reaction even when irradiated with relatively low-energy radiation such as ultraviolet light.
The photopolymerization initiator in the adhesive composition (I-3) may be the same photopolymerization initiator as that in the adhesive composition (I-1).
The pressure-sensitive adhesive composition (I-3) may contain only one kind of photopolymerization initiator, or may contain two or more kinds of photopolymerization initiators, and when the number of photopolymerization initiators is two or more, the combination and ratio thereof may be arbitrarily selected.
When a photopolymerization initiator is used, the content of the photopolymerization initiator in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass, more preferably 0.03 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable compound.
[ other additives and solvents ]
The adhesive composition (I-3) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.
Further, the adhesive composition (I-3) may also contain a solvent for the same purpose as in the adhesive composition (I-1).
Examples of the other additives and solvents in the adhesive composition (I-3) include the same additives and solvents as those in the adhesive composition (I-1).
The adhesive composition (I-3) may contain only one type of other additive and one or more types of solvent, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The content of other additives and solvents in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected depending on the type thereof.
< adhesive compositions other than the adhesive compositions (I-1) to (I-3) >
Although the adhesive composition (I-1), the adhesive composition (I-2) and the adhesive composition (I-3) have been mainly described above, the components described as the components contained in these compositions can be similarly used for all adhesive compositions except for the three adhesive compositions (in the present specification, they may be referred to as "adhesive compositions except for the adhesive compositions (I-1) to (I-3)").
Examples of the adhesive compositions other than the adhesive compositions (I-1) to (I-3) include energy ray-curable adhesive compositions and non-energy ray-curable adhesive compositions.
Examples of the non-energy ray-curable adhesive composition include an adhesive composition (I-4) containing a non-energy ray-curable adhesive resin (I-1a) such as an acrylic resin, a urethane resin, a rubber resin, a silicone resin, an epoxy resin, a polyvinyl ether, a polycarbonate, or an ester resin, and preferably an acrylic resin.
The adhesive compositions other than the adhesive compositions (I-1) to (I-3) preferably contain one or more kinds of crosslinking agents, and the content thereof may be the same as in the case of the adhesive composition (I-1) or the like.
< adhesive composition (I-4) >)
As a preferred example of the adhesive composition (I-4), there can be mentioned, for example, an adhesive composition containing the adhesive resin (I-1a) and a crosslinking agent.
[ adhesive resin (I-1a) ]
The adhesive resin (I-1a) in the adhesive composition (I-4) may be the same adhesive resin as the adhesive resin (I-1a) in the adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be one type or two or more types, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly preferably 15 to 90% by mass, based on the total mass of the adhesive composition (I-4).
[ crosslinking agent ]
When the acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth) acrylate is used as the adhesive resin (I-1a), the adhesive composition (I-4) preferably further contains a crosslinking agent.
The crosslinking agent in the adhesive composition (I-4) may be the same crosslinking agent as that in the adhesive composition (I-1).
The crosslinking agent contained in the adhesive composition (I-4) may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 25 parts by mass, and particularly preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the content of the adhesive resin (I-1 a).
[ other additives, solvents ]
The adhesive composition (I-4) may contain other additives not belonging to any of the above-mentioned components within a range not impairing the effects of the present invention.
Further, the adhesive composition (I-4) may also contain a solvent for the same purpose as in the adhesive composition (I-1).
Examples of the other additives and solvents in the adhesive composition (I-4) include the same additives and solvents as those in the adhesive composition (I-1).
The adhesive composition (I-4) may contain only one type of other additive and one or more types of solvent, and when two or more types are contained, the combination and ratio thereof may be arbitrarily selected.
The content of other additives and solvents in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected depending on the type thereof.
Method for preparing adhesive composition
The adhesive compositions other than the adhesive compositions (I-1) to (I-3), such as the adhesive compositions (I-1) to (I-3) and the adhesive composition (I-4), can be obtained by blending the above adhesive and, if necessary, components other than the above adhesive, and the like, for each component constituting the adhesive composition.
The order of addition of the components in blending is not particularly limited, and two or more components may be added simultaneously.
When the solvent is used, the solvent may be mixed with any of the components other than the solvent to dilute the components in advance, or the solvent may be mixed with the components without diluting any of the components other than the solvent to use.
The method for mixing the components at the time of blending is not particularly limited, and may be appropriately selected from the following known methods: a method of mixing by rotating a stirrer, a stirring blade, or the like; a method of mixing using a mixer; a method of mixing by applying ultrasonic waves, and the like.
The temperature and time for adding and mixing the components are not particularly limited and may be appropriately adjusted as long as the components are not deteriorated, but the temperature is preferably 15 to 30 ℃.
Intermediate layer and intermediate layer-forming composition
The intermediate layer is in the form of a sheet or a film and contains the non-silicon resin as a main component. The intermediate layer may contain only the non-silicon resin (be composed of the non-silicon resin), or may contain the non-silicon resin and components other than the non-silicon resin.
The intermediate layer can be formed using, for example, an intermediate layer-forming composition containing the non-silicone resin. The intermediate layer can be formed on a target site by, for example, applying the intermediate layer-forming composition to a surface to be formed of the intermediate layer and drying the intermediate layer as necessary.
In the intermediate layer, the ratio of the total content of one or two or more of the below-described components contained in the intermediate layer to the total mass of the intermediate layer is not more than 100 mass%.
Similarly, in the intermediate layer-forming composition, the ratio of the total content of one or two or more later-described components contained in the intermediate layer-forming composition to the total mass of the intermediate layer-forming composition is not more than 100% by mass.
The intermediate layer-forming composition can be applied by the same method as that used for applying the adhesive composition.
The drying conditions of the intermediate layer-forming composition are not particularly limited. When the composition for forming the intermediate layer contains a solvent described later, it is preferably dried by heating, and in this case, it is preferably dried at 60 to 130 ℃ for 1 to 6 minutes, for example.
The weight average molecular weight of the non-silicone resin is 100000 or less.
In order to further improve the suitability for dividing the semiconductor wafer of the semiconductor device manufacturing sheet, the weight average molecular weight of the non-silicon resin may be, for example, any one of 80000 or less, 60000 or less, and 40000 or less.
The lower limit of the weight average molecular weight of the non-silicone resin is not particularly limited, and for example, the non-silicone resin having a weight average molecular weight of 5000 or more can be more easily obtained.
The weight average molecular weight of the non-silicone resin may be appropriately adjusted within a range set by arbitrarily combining any of the lower limit values and any of the upper limit values. For example, in one embodiment, the weight average molecular weight can range anywhere from 5000 to 100000, 5000 to 80000, 5000 to 60000, and 5000 to 40000, for example.
In the present embodiment, the phrase "the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component" means "the intermediate layer contains the non-silicon resin in such an amount that the effect of containing the non-silicon resin having a weight average molecular weight of 100000 or less can be sufficiently exerted". In this regard, in the intermediate layer, the proportion of the content of the non-silicone resin with respect to the total mass of the intermediate layer (in other words, the proportion of the content of the non-silicone resin with respect to the total content of all the components excluding the solvent in the intermediate layer-forming composition) may be 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and may be, for example, any one of the ranges of 95 mass% or more, 97 mass% or more, and 99 mass% or more.
On the other hand, the ratio is 100 mass% or less.
The non-silicon resin having a weight average molecular weight of 100000 or less is not particularly limited as long as it is a resin component having no silicon atom as a constituent atom and having a weight average molecular weight of 100000 or less.
The non-silicone resin may be, for example, any of a polar resin having a polar group and a non-polar resin having no polar group.
For example, the non-silicone resin is preferably a polar resin in view of high solubility in the intermediate layer-forming composition and higher coatability of the intermediate layer-forming composition.
In the present specification, unless otherwise specified, "non-silicone resin" means the above-mentioned non-silicone resin having a weight average molecular weight of 100000 or less.
The non-silicone resin may be, for example, a homopolymer of a polymer of one monomer (in other words, having only one kind of structural unit) or a copolymer of polymers of two or more monomers (in other words, having two or more kinds of structural units).
Examples of the polar group include a carbonyloxy group (-C (═ O) -O-), an oxycarbonyl group (-O-C (═ O) -), and the like.
The polar resin may have only a structural unit having a polar group, or may have both a structural unit having a polar group and a structural unit having no polar group.
Examples of the structural unit having a polar group include a structural unit derived from vinyl acetate.
Examples of the structural unit having no polar group include structural units derived from ethylene and the like.
Where "derivatised" means that the monomer has undergone the structural change required for polymerisation.
In the polar resin, the proportion of the mass of the structural unit having a polar group to the total mass of all the structural units is preferably 5 to 70 mass%, and may be, for example, any one of 7.5 to 55 mass% and 10 to 40 mass%. In other words, in the polar resin, the proportion of the mass of the structural unit having no polar group to the total mass of all the structural units is preferably 30 to 95 mass%, and may be, for example, any one of 45 to 92.5 mass% and 60 to 90 mass%. By setting the ratio of the mass of the structural unit having a polar group to the lower limit value or more, the polar resin more remarkably has characteristics due to having a polar group. By setting the ratio of the mass of the structural unit having a polar group to the upper limit or less, the polar resin more appropriately has characteristics due to the absence of a polar group.
Examples of the polar resin include an ethylene-vinyl acetate copolymer.
Among these, the preferred polar resin is, for example, an ethylene-vinyl acetate copolymer in which the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units (in the present specification, it may be referred to as "the content of the structural unit derived from vinyl acetate") is 40% by mass or less, 30% by mass or less, 10 to 40% by mass or 10 to 30% by mass. In other words, in the preferred polar resin, for example, in the ethylene-vinyl acetate copolymer, the ratio of the mass of the structural unit derived from ethylene to the total mass of all the structural units may be 60 mass% or more, may be 70 mass% or more, may be 60 to 90 mass%, and may be 70 to 90 mass%.
The nonpolar resin is preferably a polyolefin, and examples thereof include Polyethylene (PE) such as Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), metallocene-catalyzed linear low density polyethylene (metallocene LLDPE), Medium Density Polyethylene (MDPE), and High Density Polyethylene (HDPE); polypropylene (PP), and the like.
The composition for forming an intermediate layer and the non-silicone resin contained in the intermediate layer may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
The composition for forming an intermediate layer and the non-silicone resin contained in the intermediate layer are preferably an ethylene-vinyl acetate copolymer or a polyolefin.
For example, the composition for forming an intermediate layer and the intermediate layer may contain one or two or more kinds of non-silicone resins as polar resins and not contain non-silicone resins as non-polar resins, may contain one or two or more kinds of non-silicone resins as non-polar resins and not contain non-silicone resins as polar resins, and may contain one or two or more kinds of non-silicone resins as polar resins and non-silicone resins as non-polar resins at the same time.
Preferably, the composition for forming an intermediate layer and the intermediate layer contain at least a non-silicone resin as a polar resin.
In the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin as a polar resin to the total content of the non-silicone resins may be 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be any of values of 95% by mass or more, 97% by mass or more, and 99% by mass or more, for example. By setting the ratio to the lower limit or more, the effect of using the polar resin can be more remarkably obtained.
On the other hand, the ratio is 100 mass% or less.
That is, in the composition for forming an intermediate layer and the intermediate layer, the proportion of the content of the non-silicone resin as a non-polar resin to the total content of the non-silicone resin is preferably 20% by mass or less, more preferably 10% by mass or less, and may be any of 5% by mass or less, 3% by mass or less, and 1% by mass or less, for example.
On the other hand, the ratio is 0 mass% or more.
From the viewpoint of good workability, the intermediate layer-forming composition preferably contains a solvent in addition to the non-silicone resin, and may contain a component (also referred to as an "additive" in the present specification) that does not belong to either the non-silicone resin or the solvent.
The intermediate layer may contain only the non-silicone resin or may contain both the non-silicone resin and the additive.
The additive may be any of a resin component (in this specification, sometimes referred to as "other resin component") and a non-resin component.
Examples of the other resin component include a non-silicone resin and a silicone resin having a weight average molecular weight (Mw) of more than 100000(Mw > 100000).
The non-silicone resin having a weight average molecular weight of more than 100000 is not particularly limited as long as the above conditions are satisfied.
As described later, the intermediate layer containing the silicone resin facilitates the pickup of the silicon chip with the film-like adhesive.
The silicon-based resin is not particularly limited as long as the silicon-based resin is a resin component having a silicon atom as a constituent atom. For example, the weight average molecular weight of the silicone resin is not particularly limited.
Examples of the preferable silicone resin include a resin component which exhibits a mold release action with respect to the adhesive component, and more preferably a silicone resin (a resin component having a siloxane bond (-Si-O-Si-)).
Examples of the siloxane-based resin include polydialkylsiloxane.
The number of carbon atoms of the alkyl group of the polydialkylsiloxane is preferably 1 to 20.
In the polydialkylsiloxane, the two alkyl groups bonded to one silicon atom may be the same as each other or different from each other. When two alkyl groups bonded to one silicon atom are different from each other, the combination of the two alkyl groups is not particularly limited.
Examples of the polydialkylsiloxane include polydimethylsiloxane.
The non-resin component may be, for example, any of an organic compound and an inorganic compound, and is not particularly limited.
The composition for forming an intermediate layer and the additive contained in the intermediate layer may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
For example, the composition for forming an intermediate layer and the intermediate layer may contain one or two or more resin components and not contain a non-resin component, may contain one or two or more non-resin components and not contain a resin component, and may contain one or two or more resin components and non-resin components at the same time as the additive.
When the intermediate layer-forming composition and the intermediate layer contain the additive, the proportion of the non-silicone resin content in the intermediate layer to the total mass of the intermediate layer (in other words, the proportion of the non-silicone resin content to the total content of all components excluding the solvent in the intermediate layer-forming composition) is preferably 90 to 99.99 mass%, and may be, for example, any one of 90 to 97.5 mass%, 90 to 95 mass%, and 90 to 92.5 mass%, or may be any one of 92.5 to 99.99 mass%, 95 to 99.99 mass%, and 97.5 to 99.99 mass%, or may be 92.5 to 97.5 mass%.
When the intermediate layer-forming composition and the intermediate layer contain the additive, the ratio of the content of the additive to the total mass of the intermediate layer in the intermediate layer (in other words, the ratio of the content of the additive to the total content of all components except the solvent in the intermediate layer-forming composition) is preferably 0.01 to 10% by mass, and may be, for example, any one of 2.5 to 10% by mass, 5 to 10% by mass, and 7.5 to 10% by mass, or may be any one of 0.01 to 7.5% by mass, 0.01 to 5% by mass, and 0.01 to 2.5% by mass, and may be 2.5 to 7.5% by mass.
The solvent contained in the composition for forming the intermediate layer is not particularly limited, and preferable examples of the solvent include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The intermediate layer-forming composition may contain only one kind of solvent, or may contain two or more kinds of solvents, and when the number of solvents is two or more, the combination and ratio thereof may be arbitrarily selected.
The solvent contained in the intermediate layer-forming composition is preferably tetrahydrofuran or the like, because the components contained in the intermediate layer-forming composition can be mixed more uniformly.
The content of the solvent in the intermediate layer-forming composition is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.
As described later, the preferable intermediate layer is, for example, the following intermediate layer in view of enabling easier pickup of a silicon chip with a film-like adhesive: the resin composition contains an ethylene-vinyl acetate copolymer as the non-silicone resin and a silicone compound as the additive, and the ratio of the content of the ethylene-vinyl acetate copolymer (the non-silicone resin) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical ranges described above, and the ratio of the content of the silicone compound (the additive) in the intermediate layer to the total mass of the intermediate layer is within any one of the numerical ranges described above.
Examples of such an intermediate layer include the following intermediate layers: the resin composition contains an ethylene-vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%. However, this is only one example of a preferred intermediate layer.
More preferable examples of the intermediate layer include the following intermediate layers: the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, wherein the ratio of the mass of structural units derived from vinyl acetate to the total mass of all the structural units (in other words, the content of structural units derived from vinyl acetate) in the ethylene-vinyl acetate copolymer is 10 to 40 mass%, the ratio of the content of the ethylene-vinyl acetate copolymer to the total mass of the intermediate layer in the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound to the total mass of the intermediate layer in the intermediate layer is 0.01 to 10 mass%. However, this is only one example of a more preferred intermediate layer.
In a semiconductor device manufacturing sheet, when a surface of the intermediate layer on the film-like binder side (for example, the first surface 13a of the intermediate layer 13 in fig. 1) is analyzed by X-ray Photoelectron Spectroscopy (which may be referred to as "XPS" in the present specification), the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon (which may be referred to as "the ratio of the silicon concentration" in the present specification) is preferably 1 to 20% on the basis of the molar standard of the element. By using a semiconductor device manufacturing sheet provided with such an intermediate layer, a silicon chip with a film-like adhesive can be picked up more easily as described later.
XPS analysis can be performed in the following way: the surface of the film-like adhesive side of the intermediate layer to be analyzed was set to 45 ° for X-ray irradiation angle, 20 μm Φ for X-ray beam diameter, and 4.5W for power using an X-ray photoelectron spectroscopy apparatus.
The ratio of the silicon concentration can be calculated using the following formula:
[ measured value of silicon concentration (atomic%) obtained by XPS analysis ]/{ [ measured value of carbon concentration (atomic%) obtained by XPS analysis ] + [ measured value of oxygen concentration (atomic%) obtained by XPS analysis ] + [ measured value of nitrogen concentration (atomic%) obtained by XPS analysis ] + [ measured value of silicon concentration (atomic%) obtained by XPS analysis ] + ] }. times.100
For XPS analysis, the surface of the film-like adhesive agent side intermediate layer can be subjected to XPS analysis under conditions of an irradiation angle of 45 °, an X-ray beam diameter of 20 μm Φ, and a power of 4.5W using an X-ray photoelectron spectroscopy apparatus (for example, "quanta SXM" manufactured by ULVAC, inc.).
In order to make the above-mentioned effects more remarkable, for example, the silicon concentration may be in a range of 4 to 20%, 8 to 20%, and 12 to 20%, 1 to 16%, 1 to 12%, and 1 to 8%, and 4 to 16%, and 8 to 12% on a molar basis of the element.
When XPS analysis is performed in the above-described manner, another element which does not belong to any of carbon, oxygen, nitrogen, and silicon may be detected in the surface of the intermediate layer (the surface to be analyzed by XPS). However, even if the other elements are detected, the concentration of the other elements is usually trace, and therefore, when the ratio of the silicon concentration is calculated, the ratio of the silicon concentration can be calculated with high accuracy by using the measured values of the concentrations of carbon, oxygen, nitrogen, and silicon.
The intermediate layer may be composed of one layer (single layer) or a plurality of layers of two or more layers, and in the case of being composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
As explained hereinbefore, it is preferable that the maximum value of the width of the intermediate layer is smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the base material.
The maximum value of the width of the intermediate layer may be appropriately selected in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the intermediate layer may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. These three numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to the adhesion surface of the semiconductor device manufacturing sheet of 150mm, 200mm, or 300 mm. However, as described above, when the film-like adhesive is cut by spreading the semiconductor device manufacturing sheet after dicing accompanied by formation of the modified layer in the semiconductor wafer, a plurality of semiconductor chips (semiconductor chip groups) after dicing are collectively joined as described below, and the semiconductor device manufacturing sheet is attached to these semiconductor chips.
In the present specification, unless otherwise specified, "the width of the intermediate layer" means, for example, "the width of the intermediate layer in a direction parallel to the first surface of the intermediate layer". For example, in the case of an intermediate layer having a circular planar shape, the maximum value of the width of the intermediate layer is the diameter of the circle having the planar shape.
This is also the case for semiconductor wafers. That is, the "width of the semiconductor wafer" means "the width of the semiconductor wafer in the direction parallel to the bonding surface of the semiconductor device manufacturing sheet. For example, in the case of a semiconductor wafer having a circular planar shape, the maximum value of the width of the semiconductor wafer is the diameter of the circle having the planar shape.
The maximum value of the width of the intermediate layer of 150 to 160mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 150mm in a range of not more than 10 mm.
Similarly, the maximum value of the width of the intermediate layer of 200 to 210mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 200mm in a range of not more than 10 mm.
Similarly, the maximum value of the width of the intermediate layer of 300 to 310mm is equal to or greater than the maximum value of the width of the semiconductor wafer of 300mm in a range of not more than 10 mm.
That is, in the present embodiment, for example, when the maximum value of the width of the semiconductor wafer is any one of 150mm, 200mm, and 300mm, the difference between the maximum value of the width of the intermediate layer and the maximum value of the width of the semiconductor wafer may be 0 to 10 mm.
The thickness of the intermediate layer may be appropriately selected according to the purpose, and is preferably 5 to 150 μm, more preferably 5 to 120 μm, and may be, for example, any one of 10 to 90 μm and 10 to 60 μm, or may be any one of 30 to 120 μm and 60 to 120 μm. By setting the thickness of the intermediate layer to the lower limit or more, the structure of the intermediate layer is more stabilized. By setting the thickness of the intermediate layer to the upper limit value or less, the film-like adhesive can be cut more easily during dicing and during the expansion of the semiconductor device manufacturing sheet.
The "thickness of the intermediate layer" refers to the thickness of the entire intermediate layer, and for example, the thickness of the intermediate layer composed of a plurality of layers refers to the total thickness of all the layers constituting the intermediate layer.
When the intermediate layer contains the silicone-based resin, particularly when the compatibility of the silicone-based resin with the non-silicone-based resin as a main component is low, the silicone-based resin in the intermediate layer tends to be present in both surfaces (the first surface and the surface opposite to the first surface) of the intermediate layer and in the vicinity thereof in the sheet for manufacturing a semiconductor device. Further, the stronger such tendency is, the more easily the film-like adhesive adjacent to (in direct contact with) the intermediate layer is peeled off from the intermediate layer, and as described later, the silicon chip with the film-like adhesive can be picked up more easily.
For example, when comparing intermediate layers that are different from each other only in thickness but are identical to each other in terms of composition, area of both sides, and the like other than thickness, in these intermediate layers, the proportions (mass%) of the content of the silicone-based resin with respect to the total mass of the intermediate layers are identical to each other. However, the silicone resin content (parts by mass) in the thick intermediate layer is higher than that in the thin intermediate layer. Therefore, when the silicone-based resin is likely to be biased to be present in the intermediate layer as described above, the amount of the silicone-based resin biased to be present on both surfaces (the first surface and the surface opposite to the first surface) and the vicinity thereof in the intermediate layer having a large thickness is increased as compared with the intermediate layer having a small thickness. Therefore, the pickup suitability of the silicon chip with the film-like adhesive can be adjusted by adjusting the thickness of the intermediate layer in the semiconductor device-manufacturing sheet without changing the ratio. For example, by increasing the thickness of the intermediate layer in the semiconductor device manufacturing sheet, a silicon chip with a film-like adhesive can be picked up more easily.
Film-like adhesive
The film-like adhesive has curability, preferably thermosetting, and preferably pressure-sensitive adhesiveness. A film-like adhesive having both thermosetting and pressure-sensitive adhesive properties can be attached by lightly pressing it in an uncured state against various adherends. The film-like pressure-sensitive adhesive may be one which can be attached to various adherends by softening the pressure-sensitive adhesive by heating. The film-like adhesive is cured to finally form a cured product having high impact resistance, and the cured product can maintain sufficient adhesive properties even under severe conditions of high temperature and high humidity.
When the semiconductor device manufacturing sheet is viewed from above, the area of the film-like adhesive (i.e., the area of the first surface) is preferably set to be smaller than the area of the base material (i.e., the area of the first surface) and the area of the adhesive layer (i.e., the area of the first surface) so as to be close to the area of the semiconductor wafer before dicing. In such a semiconductor device manufacturing sheet, a region not in contact with the intermediate layer and the film-like adhesive (i.e., the non-lamination region) is present in a part of the first surface of the adhesive layer. This makes it easier to expand the sheet for manufacturing a semiconductor device, and also makes it easier to cut the film-like adhesive because the force applied to the film-like adhesive during expansion is not dispersed.
The film-like adhesive can be formed using an adhesive composition containing a constituent material of the film-like adhesive. For example, a film-like adhesive can be formed on a target site by applying an adhesive composition to a surface to be formed with the film-like adhesive and drying the adhesive composition as necessary.
In the film-shaped adhesive, the ratio of the total content of one or two or more of the components to be contained in the film-shaped adhesive to the total mass of the film-shaped adhesive is not more than 100% by mass.
Similarly, in the binder composition, the ratio of the total content of one or two or more of the components contained in the binder composition, which will be described later, to the total mass of the binder composition is not more than 100% by mass.
The adhesive composition can be applied by the same method as that for the above adhesive composition.
The drying conditions of the adhesive composition are not particularly limited. When the binder composition contains a solvent described later, it is preferably dried by heating, and in this case, it is preferably dried at 70 to 130 ℃ for 10 seconds to 5 minutes, for example.
The film-like adhesive may be composed of one layer (single layer) or a plurality of layers of two or more layers, and when composed of a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of these plurality of layers is not particularly limited.
As explained hereinbefore, the maximum value of the width of the film-like adhesive is preferably smaller than the maximum value of the width of the adhesive layer and the maximum value of the width of the substrate.
The maximum value of the width of the film-like adhesive may correspond to the size of the semiconductor wafer and be the same as the maximum value of the width of the intermediate layer described above.
That is, the maximum value of the width of the film-shaped adhesive can be selected as appropriate in consideration of the size of the semiconductor wafer. For example, the maximum value of the width of the film-like adhesive may be 150 to 160mm, 200 to 210mm, or 300 to 310 mm. The three numerical ranges correspond to semiconductor wafers having a maximum value of width in a direction parallel to the bonding surface of the semiconductor device manufacturing sheet of 150mm, 200mm, or 300 mm.
In the present specification, unless otherwise specified, "the width of the film-shaped adhesive" means, for example, "the width of the film-shaped adhesive in a direction parallel to the first surface of the film-shaped adhesive". For example, in the case of a film-like adhesive having a circular planar shape, the maximum value of the width of the film-like adhesive is the diameter of a circle having the planar shape.
Unless otherwise specified, the "width of the film-like adhesive" refers to the "width of the film-like adhesive before cutting (not cutting)" in the process of manufacturing a semiconductor chip with a film-like adhesive described later, and does not refer to the width of the film-like adhesive after cutting.
The maximum value of the width of the film-like adhesive of 150 to 160mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 150mm within a range of not more than 10 mm.
Similarly, the maximum value of the width of the film-like adhesive of 200 to 210mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 200mm within a range of not more than 10 mm.
Similarly, the maximum value of the width of the film-like adhesive of 300 to 310mm means the maximum value of the width of a semiconductor wafer which is equal to or larger than 300mm within a range of not more than 10 mm.
That is, in the present embodiment, for example, when the maximum value of the width of the semiconductor wafer is any one of 150mm, 200mm, and 300mm, the difference between the maximum value of the width of the film-like adhesive and the maximum value of the width of the semiconductor wafer may be 0 to 10 mm.
In the present embodiment, the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive may be any of the above numerical value ranges.
That is, as an example of the sheet for manufacturing a semiconductor device of the present embodiment, there can be mentioned a sheet for manufacturing a semiconductor device in which the maximum value of the width of the intermediate layer and the maximum value of the width of the film-like adhesive are 150 to 160mm, 200 to 210mm, or 300 to 310 mm.
The thickness of the film-like adhesive is not particularly limited, but is preferably 1 to 30 μm, more preferably 2 to 20 μm, and particularly preferably 3 to 10 μm. By setting the thickness of the film-like pressure-sensitive adhesive to the lower limit or more, a higher adhesive force to an adherend (semiconductor chip) can be obtained. By setting the thickness of the film-like adhesive to the upper limit or less, the film-like adhesive can be cut more easily during dicing and the expansion of the semiconductor device manufacturing sheet.
The "thickness of the film-like adhesive" refers to the thickness of the entire film-like adhesive, and for example, the thickness of the film-like adhesive composed of a plurality of layers refers to the total thickness of all the layers constituting the film-like adhesive.
The adhesive composition will be described below.
Adhesive composition
A preferable adhesive composition includes, for example, an adhesive composition containing a polymer component (a) and a thermosetting component (b). Hereinafter, each component will be described.
In addition, the adhesive composition shown below is one preferable example, and the adhesive composition in the present embodiment is not limited to the examples shown below.
[ Polymer component (a) ]
The polymer component (a) is a component formed by polymerizing a polymerizable compound, and is a polymer compound for imparting film formability, flexibility, or the like to a film-like adhesive and improving adhesiveness (in other words, adhesiveness) to an object to be adhered such as a semiconductor chip. The polymer component (a) has thermoplasticity and does not have thermosetting properties. In the present specification, the polymer compound also includes a product of a polycondensation reaction.
The polymer component (a) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the polymer component (a) include acrylic resins, urethane resins, phenoxy resins, silicone resins, and saturated polyester resins.
Among these components, the polymer component (a) is preferably an acrylic resin.
In the adhesive composition, the proportion of the content of the polymer component (a) to the total content of all components except the solvent (i.e., the proportion of the content of the polymer component (a) in the film-shaped adhesive to the total mass of the film-shaped adhesive) is preferably 20 to 75 mass%, more preferably 30 to 65 mass%.
[ thermosetting component (b) ]
The thermosetting component (b) has thermosetting properties and is a component for thermally curing the film-like adhesive.
The thermosetting component (b) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Examples of the thermosetting component (b) include epoxy thermosetting resins, polyimide resins, and unsaturated polyester resins.
Among these components, the thermosetting component (b) is preferably an epoxy thermosetting resin.
O epoxy thermosetting resin
The epoxy thermosetting resin is composed of an epoxy resin (b1) and a thermosetting agent (b 2).
The epoxy thermosetting resin contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Epoxy resin (b1)
Examples of the epoxy resin (b1) include known epoxy resins, and examples thereof include polyfunctional epoxy resins, biphenyl compounds, bisphenol a diglycidyl ether and hydrogenated products thereof, o-cresol novolac epoxy resins, dicyclopentadiene epoxy resins, biphenyl epoxy resins, bisphenol a epoxy resins, bisphenol F epoxy resins, phenylene skeleton epoxy resins, and other epoxy compounds having at least two functionalities.
As the epoxy resin (b1), an epoxy resin having an unsaturated hydrocarbon group can be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor package obtained using a film-like adhesive is improved.
The epoxy resin (b1) contained in the adhesive composition and the film adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
Thermosetting agent (b2)
The thermosetting agent (b2) functions as a curing agent for the epoxy resin (b 1).
Examples of the thermosetting agent (b2) include compounds having two or more functional groups reactive with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group obtained by anhydrizing an acid group, and the like, and a phenolic hydroxyl group, an amino group, or a group obtained by anhydrizing an acid group are preferable, and a phenolic hydroxyl group or an amino group is more preferable.
Examples of the phenol curing agent having a phenolic hydroxyl group in the heat curing agent (b2) include polyfunctional phenol resins, biphenol, novolak-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type phenol resins.
Examples of the amine-based curing agent having an amino group in the thermosetting agent (b2) include Dicyandiamide (DICY).
The thermosetting agent (b2) may have an unsaturated hydrocarbon group.
The heat-curing agent (b2) contained in the adhesive composition and the film-like adhesive may be one type or two or more types, and when two or more types are used, the combination and ratio thereof may be arbitrarily selected.
In the adhesive composition and the film-like adhesive, the content of the thermosetting agent (b2) is preferably 0.1 to 500 parts by mass, more preferably 1 to 200 parts by mass, and may be, for example, any one of 1 to 100 parts by mass, 1 to 50 parts by mass, and 1 to 25 parts by mass, relative to 100 parts by mass of the content of the epoxy resin (b 1). When the content of the thermosetting agent (b2) is not less than the lower limit, the film-shaped adhesive can be more easily cured. When the content of the thermosetting agent (b2) is not more than the upper limit, the moisture absorption rate of the film-like adhesive is reduced, and the reliability of the semiconductor package obtained by using the film-like adhesive is improved.
In the adhesive composition and the film-like adhesive, the content of the thermosetting component (b) (for example, the total content of the epoxy resin (b1) and the thermosetting agent (b2)) is preferably 5 to 100 parts by mass, more preferably 5 to 75 parts by mass, particularly preferably 5 to 50 parts by mass, and may be, for example, 5 to 35 parts by mass or 5 to 20 parts by mass, based on 100 parts by mass of the content of the polymer component (a). By making the content of the thermosetting component (b) within the above range, the peeling force between the intermediate layer and the film-like adhesive is more stable.
In order to improve various physical properties of the film-shaped adhesive, the adhesive composition and the film-shaped adhesive may further contain, as necessary, other components other than the polymer component (a) and the thermosetting component (b) in addition to the polymer component (a) and the thermosetting component (b).
Preferred examples of the other components contained in the adhesive composition and the film-like adhesive include a curing accelerator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), an energy ray-curable resin (g), a photopolymerization initiator (h), and a general-purpose additive (i).
[ curing Accelerator (c) ]
The curing accelerator (c) is a component for adjusting the curing speed of the adhesive composition.
Examples of the preferable curing accelerator (c) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles (imidazole in which one or more hydrogen atoms are replaced with a group other than a hydrogen atom) such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; organic phosphines (phosphines in which one or more hydrogen atoms are substituted with an organic group), such as tributylphosphine, diphenylphosphine, and triphenylphosphine; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate (tetraphenylphosphonium tetraphenylborate) and triphenylphosphine tetraphenylboron (triphenylphosphonetetraphenyl borate).
The curing accelerator (c) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the curing accelerator (c) is used, the content of the curing accelerator (c) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the thermosetting component (b) in the adhesive composition and the film-like adhesive. By setting the content of the curing accelerator (c) to the lower limit or more, the effect of using the curing accelerator (c) can be more remarkably obtained. When the content of the curing accelerator (c) is not more than the upper limit, for example, the effect of suppressing the occurrence of segregation due to the highly polar curing accelerator (c) moving to the side of the adhesive surface with the adherend in the film-like adhesive under high-temperature and high-humidity conditions is increased, and the reliability of the semiconductor package obtained using the film-like adhesive is further improved.
[ Filler (d) ]
By containing the filler (d), the cuttability of the film-like adhesive due to spreading is further improved. Further, by containing the filler (d), the thermal expansion coefficient of the film-like adhesive can be easily adjusted, and by optimizing the thermal expansion coefficient with respect to the object to which the film-like adhesive is attached, the reliability of the semiconductor package obtained using the film-like adhesive can be further improved. Further, by containing the filler (d) in the film-shaped adhesive, the moisture absorption rate of the cured film-shaped adhesive can be reduced and the heat release property can be improved.
The filler (d) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.
Examples of the preferable inorganic filler include powders of silica, alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, and the like; beads obtained by spheroidizing these inorganic fillers; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic filler materials; glass fibers, and the like.
Among them, the inorganic filler is preferably silica or alumina.
The filler (d) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
When the filler (d) is used, the content of the filler (d) in the adhesive composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass, based on the total content of all the components except the solvent (i.e., the content of the filler (d) in the film-shaped adhesive based on the total mass of the film-shaped adhesive). By making the ratio within this range. The effects of using the filler (d) can be more remarkably obtained.
[ coupling agent (e) ]
The film-like pressure-sensitive adhesive containing the coupling agent (e) improves the adhesiveness and adherence to an adherend. Further, by containing the coupling agent (e), the water resistance of the cured product of the film-like adhesive is improved, and the heat resistance is not impaired. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.
The coupling agent (e) is preferably a compound having a functional group capable of reacting with the functional group of the polymer component (a), the thermosetting component (b), or the like, and more preferably a silane coupling agent.
The adhesive composition and the film-like adhesive may contain only one kind of the coupling agent (e), or two or more kinds thereof, and when two or more kinds thereof are contained, the combination and ratio thereof may be arbitrarily selected.
When the coupling agent (e) is used, the content of the coupling agent (e) is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total content of the polymer component (a) and the thermosetting component (b) in the adhesive composition and the film-like adhesive. When the content of the coupling agent (e) is not less than the lower limit, the effects of using the coupling agent (e) can be more remarkably obtained, for example, the dispersibility of the filler (d) in the resin is improved, and the adhesion between the film-like pressure-sensitive adhesive and the adherend is improved. By making the content of the coupling agent (e) the upper limit value or less, the generation of outgas (outgas) can be further suppressed.
[ crosslinking agent (f) ]
When a component having a functional group such as a vinyl group, (meth) acryloyl group, amino group, hydroxyl group, carboxyl group, or isocyanate group, which can be bonded to another compound, is used as the polymer component (a), the adhesive composition and the film-shaped adhesive may contain a crosslinking agent (f). The crosslinking agent (f) is a component for bonding and crosslinking the functional group in the polymer component (a) with another compound, and the initial adhesive force and cohesive force of the film-shaped adhesive can be adjusted by crosslinking in the above manner.
Examples of the crosslinking agent (f) include an organic polyisocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), an aziridine crosslinking agent (a crosslinking agent having an aziridine group), and the like.
When an organic polyisocyanate compound is used as the crosslinking agent (f), a hydroxyl group-containing polymer is preferably used as the polymer component (a). When the crosslinking agent (f) has an isocyanate group and the polymer component (a) has a hydroxyl group, a crosslinked structure can be easily introduced into the film-shaped adhesive by the reaction of the crosslinking agent (f) with the polymer component (a).
The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be one kind alone, or two or more kinds thereof, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
When the crosslinking agent (f) is used, the content of the crosslinking agent (f) in the adhesive composition is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.3 to 5 parts by mass, relative to 100 parts by mass of the content of the polymer component (a). By setting the content of the crosslinking agent (f) to the lower limit or more, the effect of using the crosslinking agent (f) can be more remarkably obtained. By setting the content of the crosslinking agent (f) to the upper limit value or less, excessive use of the crosslinking agent (f) can be suppressed.
Energy ray-curable resin (g)
By incorporating the energy ray-curable resin (g) in the adhesive composition and the film-like adhesive, the properties of the film-like adhesive can be changed by irradiation with energy rays.
The energy ray-curable resin (g) is obtained from an energy ray-curable compound.
Examples of the energy ray-curable compound include compounds having at least one polymerizable double bond in the molecule, and preferably acrylate compounds having a (meth) acryloyl group.
The energy ray-curable resin (g) contained in the adhesive composition may be one kind only, or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the energy ray-curable resin (g) is used, the content of the energy ray-curable resin (g) in the adhesive composition is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass, based on the total mass of the adhesive composition.
[ photopolymerization initiator (h) ]
When the adhesive composition and the film-like adhesive contain the energy ray-curable resin (g), the adhesive composition and the film-like adhesive may contain a photopolymerization initiator (h) in order to effectively promote the polymerization reaction of the energy ray-curable resin (g).
Examples of the photopolymerization initiator (h) in the adhesive composition include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 2, 2-dimethoxy-1, 2-diphenylethane-1-one; acylphosphine oxide compounds such as phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; sulfides such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; alpha-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; a peroxide compound; diketone compounds such as diacetyl; benzil; dibenzoyl; benzophenone; 2, 4-diethylthioxanthone; 1, 2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone; quinone compounds such as 1-chloroanthraquinone and 2-chloroanthraquinone.
Examples of the photopolymerization initiator (h) include photosensitizers such as amines.
The photopolymerization initiator (h) contained in the adhesive composition may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
When the photopolymerization initiator (h) is used, the content of the photopolymerization initiator (h) in the adhesive composition is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 2 to 5 parts by mass, relative to 100 parts by mass of the energy ray-curable resin (g).
[ general additive (i) ]
The general-purpose additive (i) may be any known additive, and may be arbitrarily selected according to the purpose, and is not particularly limited, and preferable general-purpose additives (i) include, for example, a plasticizer, an antistatic agent, an antioxidant, a colorant (dye, pigment), a gettering agent (gettering agent), and the like.
The general-purpose additive (i) contained in the adhesive composition and the film-like adhesive may be one kind or two or more kinds, and when two or more kinds are contained, the combination and ratio thereof may be arbitrarily selected.
The content of the adhesive composition and the film-like adhesive is not particularly limited, and may be appropriately selected according to the purpose.
[ solvent ]
The adhesive composition preferably further contains a solvent. The workability of the adhesive composition containing a solvent is improved.
The solvent is not particularly limited, and preferable examples thereof include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), and 1-butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
The binder composition may contain only one kind of solvent, or two or more kinds of solvents, and when two or more kinds of solvents are contained, the combination and ratio thereof may be arbitrarily selected.
The solvent contained in the pressure-sensitive adhesive composition is preferably methyl ethyl ketone or the like, because the components contained in the pressure-sensitive adhesive composition can be mixed more uniformly.
The content of the solvent in the adhesive composition is not particularly limited, and may be appropriately selected depending on the kind of the component other than the solvent, for example.
Preparation method of adhesive composition
The adhesive composition can be obtained by blending the respective components for constituting the adhesive composition.
The adhesive composition can be prepared, for example, by the same method as in the above-described preparation of the adhesive composition, except that the kinds of blending components are different.
Manufacturing method of semiconductor device manufacturing wafer
The semiconductor device manufacturing sheet can be manufactured by stacking the layers so that the layers are in a corresponding positional relationship. The formation method of each layer is the same as that described above.
For example, the semiconductor device manufacturing sheet can be manufactured by: the base material, the adhesive layer, the intermediate layer, and the film-like adhesive are prepared in advance, and they are laminated in this order.
However, this is only one example of a method of manufacturing a sheet for semiconductor device fabrication.
The semiconductor device manufacturing sheet can be manufactured, for example, by: two or more kinds of intermediate laminated bodies each composed of a plurality of layers laminated to constitute the sheet for manufacturing a semiconductor device are prepared in advance, and these intermediate laminated bodies are bonded to each other. The structure of the intermediate laminate may be appropriately selected arbitrarily. For example, a first intermediate laminate (corresponding to the support sheet) having a structure in which a base material and an adhesive layer are laminated and a second intermediate laminate having a structure in which an intermediate layer and a film-like adhesive are laminated are prepared in advance, and the adhesive layer in the first intermediate laminate and the intermediate layer in the second intermediate laminate can be bonded to each other to produce a semiconductor device production sheet.
However, this is also only one example of a method of manufacturing a sheet for semiconductor device fabrication.
As the semiconductor device manufacturing sheet, for example, as shown in fig. 1, when a semiconductor device manufacturing sheet in which both the area of the first surface of the intermediate layer and the area of the first surface of the film-like adhesive are smaller than the area of the first surface of the adhesive layer and the area of the first surface of the substrate is manufactured, a step of processing the intermediate layer and the film-like adhesive into a desired size may be added at any stage of the manufacturing method. For example, in the manufacturing method using the second intermediate laminate, the semiconductor device manufacturing sheet can be manufactured by adding a step of processing the intermediate layer and the film-like adhesive in the second intermediate laminate into a desired size.
In the case of producing a semiconductor device-producing sheet having a release film provided on a film-like adhesive, for example, the semiconductor device-producing sheet may be produced by producing a film-like adhesive on a release film and laminating the remaining layers while maintaining this state, or the semiconductor device-producing sheet may be produced by laminating a release film on a film-like adhesive after all of the substrate, the adhesive layer, the intermediate layer, and the film-like adhesive are laminated. The release film may be removed at a desired stage until the semiconductor device manufacturing sheet is used.
The sheet for manufacturing a semiconductor device, which is provided with another layer that is not one of the substrate, the adhesive layer, the intermediate layer, the film-like adhesive, and the release film, can be manufactured by adding a step of forming the other layer and laminating the layers at an appropriate timing in the above-described manufacturing method.
Examples of preferable semiconductor device-manufacturing sheets according to this embodiment include:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer and the film-like adhesive on the substrate in this order,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the proportion of the non-silicon resin content to the total mass of the intermediate layer is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
As another example of a preferable semiconductor device-manufacturing sheet of this embodiment, there can be mentioned:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer and the film-like adhesive on the substrate in this order,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the intermediate layer contains an ethylene-vinyl acetate copolymer or a polyolefin as the non-silicone resin,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the proportion of the non-silicon resin content to the total mass of the intermediate layer is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin with respect to the total content of the non-silicone resin may be any one of 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, and 99% by mass or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
As another example of a preferable semiconductor device-manufacturing sheet of this embodiment, there can be mentioned:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer and the film-like adhesive on the substrate in this order,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin,
in the ethylene-vinyl acetate copolymer, the ratio of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is in the range of 10-40% by mass and 10-30% by mass, the ratio of the mass of the structural unit derived from ethylene to the total mass of all the structural units is in the range of 60-90% by mass and 70-90% by mass,
in the intermediate layer, the content of the ethylene-vinyl acetate copolymer is 90-99.99% by mass relative to the total mass of the intermediate layer,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the proportion of the non-silicon resin content to the total mass of the intermediate layer is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in the range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
As another example of a preferable semiconductor device-manufacturing sheet of this embodiment, there can be mentioned:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer and the film-like adhesive on the substrate in this order,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the proportion of the non-silicon resin content to the total mass of the intermediate layer is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is any one of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
when the surface of the intermediate layer on the film-shaped adhesive agent side is analyzed by X-ray photoelectron spectroscopy, the ratio of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen and silicon is in any one range of 1-20%, 4-16% and 8-12%, and the surface resistivity of the surface of the film-shaped adhesive agent on the intermediate layer side is 1X 1013Omega is less than or equal to.
As another example of a preferable semiconductor device-manufacturing sheet of this embodiment, there can be mentioned:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer and the film-like adhesive on the substrate in this order,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component, and further contains a silicon resin,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the content of the non-silicon resin is in any range of 90-99.99 mass%, 90-97.5 mass%, 90-95 mass% and 90-92.5 mass% relative to the total mass of the intermediate layer,
in the intermediate layer, the content of the silicone resin is in any range of 0.01-10 mass%, 2.5-10 mass%, 5-10 mass%, and 7.5-10 mass% with respect to the total mass of the intermediate layer,
wherein the ratio of the total content of the non-silicon resin and the silicon resin in the intermediate layer to the total mass of the intermediate layer is not more than 100% by mass,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
As another example of a preferable semiconductor device-manufacturing sheet of this embodiment, there can be mentioned:
a sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by sequentially laminating the adhesive layer, the intermediate layer and the film-like adhesive on the base material,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicon resin having a weight average molecular weight of 100000 or less as a main component, and further contains a silicon resin,
the intermediate layer contains at least a polar resin as the non-silicone resin,
in the intermediate layer, the content of the non-silicon resin is in any range of 90-99.99 mass%, 90-97.5 mass%, 90-95 mass%, and 90-92.5 mass% with respect to the total mass of the intermediate layer,
in the intermediate layer, the ratio of the content of the silicone resin to the total mass of the intermediate layer is in any range of 0.01 to 10 mass%, 2.5 to 10 mass%, 5 to 10 mass%, and 7.5 to 10 mass%,
wherein the ratio of the total content of the non-silicon resin and the silicon resin in the intermediate layer to the total mass of the intermediate layer is not more than 100% by mass,
in the intermediate layer, the proportion of the content of the non-silicone resin as the polar resin to the total content of the non-silicone resin is any one of 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, and 99 mass% or more,
in the polar resin, the ratio of the mass of the structural unit having a polar group to the total mass of all the structural units is in a range of 5 to 70 mass%, 7.5 to 55 mass%, and 10 to 40 mass%,
the thickness of the intermediate layer is within any range of 5 to 150 μm, 5 to 120 μm, 30 to 120 μm and 60 to 120 μm,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
Method of using sheet for semiconductor device fabrication (method of fabricating semiconductor chip with film-like adhesive)
The sheet for manufacturing a semiconductor device can be used in manufacturing a semiconductor chip with a film-like adhesive in a manufacturing process of a semiconductor device.
A method of using the sheet for manufacturing a semiconductor device (a method of manufacturing a semiconductor chip with a film-like adhesive) will be described in detail below with reference to the drawings.
Fig. 3A, 3B, and 3C are cross-sectional views schematically illustrating an example of a method of using a semiconductor device manufacturing sheet, and show a case where the semiconductor device manufacturing sheet is used after being attached to a semiconductor wafer. In this method, a semiconductor device manufacturing sheet is used as a dicing die.
The method for manufacturing a semiconductor chip with a film-like adhesive of the present embodiment includes:
a step (a1) of attaching the back surface of a semiconductor wafer to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet of the embodiment to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive, and the semiconductor wafer are laminated in this order;
a step (A2) of cutting the film-like adhesive agent to obtain a semiconductor chip with the film-like adhesive agent while the semiconductor wafer is being divided; and
and a step (A3) of pulling the semiconductor chip with the film-like pressure-sensitive adhesive off the base material, the pressure-sensitive adhesive layer, and the intermediate layer and picking up the semiconductor chip.
The sheet 101 for manufacturing a semiconductor device shown in fig. 1 is taken as an example, and a method of using the sheet will be described.
First, as shown in fig. 3A, the semiconductor device manufacturing sheet 101 with the release film 15 removed is heated, and the film-like adhesive 14 is attached to the back surface 9b 'of the semiconductor wafer 9' (step (a 1)).
Reference numeral 9a 'denotes a circuit forming surface of the semiconductor wafer 9'.
The heating temperature when the semiconductor device manufacturing sheet 101 is bonded is not particularly limited, but is preferably 40 to 70 ℃ from the viewpoint of further improving the heat bonding stability of the semiconductor device manufacturing sheet 101.
Width W of intermediate layer 13 in semiconductor device manufacturing sheet 10113Maximum value of (d) and width W of film-like adhesive 1414Is completely equal to the width W of the semiconductor wafer 99’The maximum values of (a) are the same or the errors are slight but almost the same although they are different.
For example, when the width W of the semiconductor wafer 99’Has a maximum value of 150mm, the width W of the intermediate layer 1313Maximum value of (d) and width W of film-like adhesive 1414The maximum value of (a) is preferably 150 to 160mm when the width W of the semiconductor wafer 99’Has a maximum value of 200mm, the width W of the intermediate layer 1313Maximum value of (d) and width W of film-like adhesive 1414The maximum value of (a) is preferably 200 to 210mm when the width W of the semiconductor wafer 99’At a maximum value of 300mm, the width W of the intermediate layer 1313Maximum value of (d) and width W of film-like adhesive 1414The maximum value of (A) is preferably 300 to 310 mm.
Thus, in the present embodiment, the width W of the intermediate layer 1313Maximum value of (d) and width W of the semiconductor wafer 99’The difference between the maximum values of (a) and (b), and the width W of the film-like adhesive 1414Maximum value of (d) and width W of the semiconductor wafer 99’The difference between the maximum values of (a) and (b) may be 0 to 10 mm.
Wherein the width W of the semiconductor wafer 99’For example, the width of the semiconductor wafer 9 'in a direction parallel to the back surface 9 b' thereof.
Then, the laminate of the semiconductor device-manufacturing sheet 101 and the semiconductor wafer 9 'obtained above is cut (diced) with a blade from the circuit-forming surface 9 a' side of the semiconductor wafer 9 ', whereby the semiconductor wafer 9' is divided and the film-like adhesive 14 is cut (step a 2).
The blade cutting can be performed by a known method. For example, in the semiconductor device manufacturing sheet 101, the region (the non-lamination region) in the vicinity of the peripheral portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 is fixed to a jig (not shown) such as a ring frame, and then the semiconductor wafer 9' can be divided and the film-like adhesive 14 can be cut by using a dicing blade.
As shown in fig. 3B, in this step, a plurality of semiconductor chips 914 with a film-like adhesive are obtained, each of which includes the semiconductor chip 9 and the film-like adhesive 140 provided on the rear surface 9B of the semiconductor chip 9 after cutting. The semiconductor chips 914 with the film adhesive are aligned and fixed to the intermediate layer 13 in the laminate sheet 10, and constitute a semiconductor chip group 910 with a film adhesive.
The rear side 9b of the semiconductor chip 9 corresponds to the rear side 9b 'of the semiconductor wafer 9'. In fig. 3B, reference numeral 9a denotes a circuit formation surface of the semiconductor chip 9, and corresponds to the circuit formation surface 9a 'of the semiconductor wafer 9'.
When the dicing is performed, it is preferable that the entire region in the thickness direction of the film-like adhesive 14 is cut by cutting the entire region in the thickness direction of the semiconductor wafer 9' with a blade into the middle region of the intermediate layer 13 from the first surface 14a of the film-like adhesive 14, thereby cutting the entire region in the thickness direction of the film-like adhesive 14 without cutting the adhesive layer 12.
That is, when dicing, it is preferable that the laminate of the semiconductor device-manufacturing sheet 101 and the semiconductor wafer 9 ' is cut by a blade from the circuit-forming surface 9a ' of the semiconductor wafer 9 ' at least to the first surface 13a of the intermediate layer 13 and not to the surface of the intermediate layer 13 opposite to the first surface 13a (i.e., the contact surface with the adhesive layer 12) in the lamination direction.
In this step, the blade can be easily prevented from reaching the base material 11, and the generation of chips from the base material 11 can be suppressed. In addition, by making the main component of the intermediate layer 13 cut by the blade a non-silicone resin having a weight average molecular weight of 100000 or less, particularly a weight average molecular weight of 100000 or less, it is possible to suppress the generation of chips from the intermediate layer 13.
The conditions for cutting by the blade may be appropriately adjusted according to the purpose, and are not particularly limited.
Generally, the rotating speed of the blade is preferably 15000-50000 rpm, and the moving speed of the blade is preferably 5-75 mm/s.
As shown in fig. 3C, after the dicing, the semiconductor chip 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminate sheet 10 and picked up (step (a 3)). Here, a case is shown in which the semiconductor chip 914 with a film-like adhesive is pulled away in the direction of arrow P using a separating device 7 such as a vacuum chuck. In addition, the separating device 7 is not shown in cross section here.
The semiconductor chip 914 with the film-like adhesive can be picked up by a known method.
In the first surface 13a of the intermediate layer 13, when the ratio of the silicon concentration is 1 to 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily.
For example, when the intermediate layer 13 contains an ethylene-vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.
As a preferred embodiment of the method for manufacturing a semiconductor chip with a film-like adhesive described above, there is, for example, a method for manufacturing a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip,
the sheet for manufacturing a semiconductor device comprises the substrate, an adhesive layer, an intermediate layer, and a film-like adhesive,
the manufacturing method comprises the following steps: heating the semiconductor device manufacturing sheet and adhering the film-like adhesive to the back surface of the semiconductor wafer; cutting the semiconductor wafer into the entire region in the thickness direction thereof from the circuit forming surface side of the semiconductor wafer to which the film-shaped adhesive is attached, thereby producing the semiconductor chip, and cutting the film-shaped adhesive into the semiconductor device manufacturing sheet in the thickness direction thereof from the film-shaped adhesive side to a middle region of the intermediate layer, thereby cutting the film-shaped adhesive without cutting the adhesive into the adhesive layer, thereby obtaining a semiconductor chip group with the film-shaped adhesive, in which a plurality of the semiconductor chips with the film-shaped adhesive are aligned on the intermediate layer; and a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, it may be referred to as "manufacturing method 1").
Fig. 4A, 4B, and 4C are cross-sectional views schematically illustrating an example of a method for manufacturing a semiconductor chip that is a target of use of a sheet for manufacturing a semiconductor device, and show a case where a semiconductor chip is manufactured by performing dicing accompanied by formation of a modified layer in a semiconductor wafer.
Fig. 5A, 5B, and 5C are cross-sectional views schematically illustrating another example of a method of using a sheet for manufacturing a semiconductor device, and show a case where the sheet for manufacturing a semiconductor device is used after being attached to a semiconductor chip. In this method, the semiconductor device manufacturing sheet is used as a solid wafer.
The method for manufacturing a semiconductor chip with a film-like adhesive of the present embodiment includes: a step (B1) of attaching the back surfaces of the semiconductor chip groups, in which the plurality of semiconductor chips are aligned, to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet in the above embodiment, to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive, and the semiconductor chip groups are sequentially laminated;
a step (B2) for cutting the film-like adhesive to obtain a semiconductor chip with the film-like adhesive; and
and a step (B3) of pulling the semiconductor chip with the film-like adhesive off the base material, the adhesive layer, and the intermediate layer and picking up the semiconductor chip.
The sheet 101 for manufacturing a semiconductor device shown in fig. 1 is taken as an example, and a method of using the sheet will be described.
First, before using the semiconductor device manufacturing sheet 101, as shown in fig. 4A, a semiconductor wafer 9 'is prepared, and a back-grinding tape (also referred to as a "surface protection tape") 8 is attached to the circuit forming surface 9 a'.
In FIG. 4A, symbol W9’Indicating the width of the semiconductor wafer 9'.
Then, laser light (not shown) is irradiated so as to be focused on a focal point set in the semiconductor wafer 9 ', and as shown in fig. 4B, a modified layer 90 ' is formed in the semiconductor wafer 9 '.
The semiconductor wafer 9 ' is preferably irradiated with the laser light from the back surface 9b ' side of the semiconductor wafer 9 '.
The position of the focal point at this time is a pre-dividing (dicing) position of the semiconductor wafer 9 ', and is set so that a desired size, shape, and number of semiconductor chips can be obtained from the semiconductor wafer 9'.
Then, the back surface 9b 'of the semiconductor wafer 9' is polished by a polishing machine (not shown). Thus, the thickness of the semiconductor wafer 9 'is adjusted to a target value, and the semiconductor wafer 9' is divided at the formation portion of the modified layer 90 'by using the force applied to the semiconductor wafer 9' at the time of polishing, thereby producing a plurality of semiconductor chips 9 as shown in fig. 4C.
The modified layer 90 ' of the semiconductor wafer 9 ' is different from the other portions of the semiconductor wafer 9 ', and the modified layer 90 ' of the semiconductor wafer 9 ' is modified by irradiation with laser light, and the intensity is weakened. Therefore, by applying a force to the semiconductor wafer 9 ' on which the modified layer 90 ' is formed, the modified layer 90 ' is applied with a force, and the semiconductor wafer 9 ' is cracked at the portion of the modified layer 90 ', thereby obtaining a plurality of semiconductor chips 9.
In this way, the semiconductor chip 9 to be used as the semiconductor device manufacturing sheet 101 can be obtained. More specifically, in this step, the semiconductor chip group 901 can be obtained in which the plurality of semiconductor chips 9 are fixed to the back-grinding tape 8 in an aligned state.
When the semiconductor chip group 901 is viewed from above in a downward direction, a planar shape formed by connecting outermost portions of the semiconductor chip group 901 (in this specification, such a planar shape may be simply referred to as a "planar shape of the semiconductor chip group") is completely the same as a planar shape of the semiconductor wafer 9 ' when the semiconductor wafer 9 ' is viewed from above in the same manner, or a difference between planar shapes of both is negligible, and it can be said that the planar shape of the semiconductor chip group 901 is substantially the same as the planar shape of the semiconductor wafer 9 '.
Therefore, as shown in fig. 4C, the width of the planar shape of the semiconductor chip group 901 and the width W of the semiconductor wafer 9' can be regarded as9’The same is true. Further, it can be regarded as the maximum value of the width of the planar shape of the semiconductor chip group 901 and the width W of the semiconductor wafer 99’The maximum values of (a) are the same.
Note that, although the semiconductor chips 9 can be produced from the semiconductor wafer 9 'as intended, the semiconductor chips 9 may not be divided in a partial region of the semiconductor wafer 9' depending on the conditions for polishing the back surface 9b 'of the semiconductor wafer 9'.
Then, using the semiconductor chip 9 (semiconductor chip group 901) obtained above, a semiconductor chip with a film-like adhesive is manufactured.
First, as shown in fig. 5A, one semiconductor device-manufacturing sheet 101 with the release film 15 removed is heated, and the film-like adhesive 14 is applied to the back surfaces 9B of all the semiconductor chips 9 in the semiconductor chip group 901 (step (B1)). The film-like adhesive 14 may be applied to a completely undivided semiconductor wafer.
Width W of intermediate layer 13 in semiconductor device manufacturing sheet 10113Maximum value of (d) and width W of film-like adhesive 1414Is equal to the width W of the semiconductor wafer 99’(in other words, the width of the semiconductor chip group 901)The same or slightly, though different, but almost the same error.
Namely, the width W of the intermediate layer 1313The relationship between the maximum value of (b) and the maximum value of the width of the semiconductor chip group 901 may be the width W of the intermediate layer 13 explained hereinbefore13Maximum value of (d) and width W of the semiconductor wafer 99’The same relationship is used between the maximum values of (a). Further, the width W of the film-like adhesive 1414May be related to the width W of the film-like adhesive 1414Maximum value of (d) and width W of the semiconductor wafer 99’The same relationship is used between the maximum values of (a).
The film-like adhesive 14 (semiconductor device manufacturing sheet 101) can be applied to the semiconductor chip group 901 in this case by the same method as that for the film-like adhesive 14 (semiconductor device manufacturing sheet 101) applied to the semiconductor wafer 9 'in the above-described manufacturing method 1, except that the semiconductor chip group 901 is used instead of the semiconductor wafer 9'.
Then, the back grinding tape 8 is removed from the semiconductor chip group 901 in the fixed state. Then, as shown in fig. 5B, the semiconductor device-manufacturing sheet 101 is stretched in a direction parallel to the surface thereof (for example, the first surface 12a of the adhesive layer 12) while being cooled, thereby spreading. Therein, with arrow E1The direction of expansion of the semiconductor device manufacturing sheet 101 is shown. The film-like adhesive 14 is spread in the above manner and cut along the outer periphery of the semiconductor chip 9 (step (B2)).
Through this step, a plurality of semiconductor chips 914 with a film-like adhesive, each including the semiconductor chip 9 and the cut film-like adhesive 140 provided on the back surface 9b thereof, can be obtained. The semiconductor chips 914 with the film adhesive are aligned and fixed to the intermediate layer 13 in the laminate sheet 10, thereby constituting a semiconductor chip group 910 with a film adhesive.
The film-adhesive-attached semiconductor chip 914 and the film-adhesive-attached semiconductor chip group 910 obtained here are basically the same as the film-adhesive-attached semiconductor chip 914 and the film-adhesive-attached semiconductor chip group 910 obtained by the manufacturing method 1 described above.
As described above, when a partial region of the semiconductor wafer 9 'is not divided into the semiconductor chips 9 at the time of dividing the semiconductor wafer 9', the partial region can be divided into the semiconductor chips by performing the present step.
The temperature of the semiconductor device manufacturing sheet 101 is preferably set to-5 to 5 ℃. By cooling and expanding (cold expanding) the semiconductor device manufacturing sheet 101 in this manner, the film-like adhesive 14 can be cut more easily and accurately.
The expansion of the semiconductor device manufacturing sheet 101 can be performed by a known method. For example, the semiconductor device-manufacturing sheet 101 may be expanded by fixing a region (the non-lamination region) in the vicinity of the peripheral portion where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 in the semiconductor device-manufacturing sheet 101 to a jig (not shown) such as a ring frame, and then pushing the entire region of the semiconductor device-manufacturing sheet 101 where the intermediate layer 13 and the film-like adhesive 14 are laminated from the substrate 11 side in the direction of the adhesive layer 12 from the substrate 11.
In fig. 5B, the non-laminated region where the intermediate layer 13 and the film-like adhesive 14 are not laminated in the first surface 12a of the adhesive layer 12 is almost parallel to the first surface 13a of the intermediate layer 13, but in a state of being spread by the push-up of the semiconductor device manufacturing sheet 101 as described above, the non-laminated region includes an inclined surface whose height decreases as it approaches the outer periphery of the adhesive layer 12 in a direction opposite to the push-up direction.
In this step, by providing the semiconductor device manufacturing sheet 101 with the intermediate layer 13 (in other words, by providing the film-like adhesive 14 before cutting on the intermediate layer 13), the film-like adhesive 14 can be cut at a target portion (in other words, along the outer periphery of the semiconductor chip 9) with high accuracy, and thus a cutting failure can be suppressed.
As shown in fig. 5C, after the spreading, the semiconductor chip 914 with the film-like adhesive is pulled away from the intermediate layer 13 in the laminate sheet 10 and picked up (step (B3)).
The pickup at this time can be performed by the same method as the pickup in the above-described manufacturing method 1, and the pickup suitability is also the same as the pickup suitability in the manufacturing method 1.
For example, in this step, when the ratio of the silicon concentration in the first surface 13a of the intermediate layer 13 is 1 to 20%, the semiconductor chip 914 with the film adhesive can be picked up more easily.
Further, when the intermediate layer 13 contains, for example, an ethylene-vinyl acetate copolymer as the non-silicone resin and a siloxane compound as the additive, and the ratio of the content of the ethylene-vinyl acetate copolymer in the intermediate layer to the total mass of the intermediate layer is 90 to 99.99 mass%, and the ratio of the content of the siloxane compound in the intermediate layer to the total mass of the intermediate layer is 0.01 to 10 mass%, the semiconductor chip 914 with a film adhesive can be picked up more easily.
As a preferred embodiment of the method for manufacturing a semiconductor chip with a film-like adhesive described above, there is, for example, a method for manufacturing a semiconductor chip with a film-like adhesive, which includes a semiconductor chip and a film-like adhesive provided on a back surface of the semiconductor chip,
the sheet for manufacturing a semiconductor device comprises the substrate, an adhesive layer, an intermediate layer, and a film-like adhesive,
the manufacturing method comprises the following steps: irradiating a semiconductor wafer with laser light so as to focus on a focal point set in the semiconductor wafer, thereby forming a modified layer in the semiconductor wafer; a step of obtaining a semiconductor chip group in which a plurality of semiconductor chips are aligned by grinding the back surface of the semiconductor wafer on which the modified layer is formed and dividing the semiconductor wafer at a portion where the modified layer is formed by a force applied to the semiconductor wafer during grinding; a step of heating the semiconductor device manufacturing sheet while attaching the film-like adhesive to the back surfaces of all the semiconductor chips in the semiconductor chip group; a step of cooling the semiconductor device manufacturing sheet having the semiconductor chips attached thereto and stretching the sheet in a direction parallel to the surface thereof to cut the film-like adhesive along the outer peripheries of the semiconductor chips, thereby obtaining a plurality of semiconductor chip groups each having the film-like adhesive and each having the semiconductor chips arranged on the intermediate layer; and a step of pulling the semiconductor chip with the film-like adhesive from the intermediate layer and picking up the semiconductor chip (in this specification, it may be referred to as "manufacturing method 2").
Although the method of using the semiconductor device-manufacturing sheet 101 shown in fig. 1 has been described as an example of any of the manufacturing methods 1 and 2, the semiconductor device-manufacturing sheet of the present embodiment can be similarly used in other cases. In this case, if necessary, the semiconductor device manufacturing sheet may be used by adding other steps as appropriate based on the difference in the structure between the semiconductor device manufacturing sheet and the semiconductor device manufacturing sheet 101.
In addition to the case of the manufacturing method 1 and the manufacturing method 2, after the semiconductor chip group with the film-like adhesive is obtained, the laminated sheet may be spread in a direction parallel to the surface (first surface) of the adhesive layer on the intermediate layer side before the semiconductor chip with the film-like adhesive is picked up, and the peripheral portion of the semiconductor chip without the film-like adhesive (the semiconductor chip group with the film-like adhesive) in the laminated sheet may be further heated while maintaining this state.
This makes it possible to shrink the peripheral portion and to sufficiently widen a distance between adjacent semiconductor chips in the laminate sheet, that is, a notch width, and to maintain the notch width with high uniformity. Further, the semiconductor chip with the film-like adhesive can be picked up more easily.
Examples
The present invention will be described in more detail below with reference to specific examples. However, the present invention is not limited to the examples shown below.
Raw material for preparing adhesive composition
The raw materials used to prepare the adhesive composition are shown below.
[ Polymer component (a) ]
(a) -1: an acrylic resin (weight average molecular weight 800000, glass transition temperature 9 ℃) obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass).
[ epoxy resin (b1) ]
(b1) -1: an acryl-added cresol novolac type epoxy resin ("CNA 147" manufactured by Nippon Kayaku co., ltd., epoxy equivalent of 518g/eq, number average molecular weight of 2100, unsaturated group content equivalent to epoxy group) was used.
[ Heat-curing agent (b2) ]
(b2) -1: aralkyl type phenol resin ("Milex XLC-4L" manufactured by Mitsui Chemicals, Inc., number average molecular weight 1100, softening point 63 ℃ C.)
[ Filler (d) ]
(d) -1: spherical silica (YA 050C-MJE manufactured by Admatech corporation, average particle diameter 50nm, methacryl silane-treated product)
[ coupling agent (e) ]
(e) -1: silane coupling agent, 3-glycidyloxypropylmethyldiethoxysilane ("KBE-402" manufactured by Shin-Etsu Silicone Co., Ltd.)
[ crosslinking agent (f) ]
(f) -1: toluene diisocyanate crosslinking agent ("CORONATE L" manufactured by TOSOH CORPORATION)
[ antistatic agent (g) ]
(g) -1: reduced graphene oxide ("N002-PDR" manufactured by Angstrom Material)
[ example 1]
Production of wafer for semiconductor device fabrication
< production of substrate >
Low density polyethylene ("sumikanene L705" manufactured by Sumitomo Chemical co., ltd.) was melted using an extruder, the melt was extruded by a T-die method, and the extrudate was biaxially stretched using a chill roll, thereby obtaining a base material (thickness of 110 μm) made of LDPE.
< preparation of adhesive layer >
A non-energy ray-curable adhesive composition containing an acrylic resin (oribian BPS 6367X, manufactured by ltd.) (100 parts by mass), a crosslinking agent (toyoche co, manufactured by ltd.) (1 part by mass) as an adhesive resin (I-1a) was prepared.
Then, using a release film obtained by subjecting one surface of the polyethylene terephthalate film to a release treatment by a silicone treatment, the obtained adhesive composition was applied to the release-treated surface, and dried by heating at 100 ℃ for 2 minutes, thereby producing a non-energy-ray-curable adhesive layer (thickness: 10 μm).
< preparation of intermediate layer >
An ethylene-vinyl acetate copolymer (EVA, weight average molecular weight of 30000, content of structural units derived from vinyl acetate 25 mass%) (15g) was dissolved in 85g of tetrahydrofuran at ordinary temperature, and a siloxane compound (polydimethylsiloxane, "BYK-333" manufactured by BYK Japan KK., chemical formula "-Si (-CH) in one molecule was added to the resulting solution3)2The number of the structural units represented by-O- "is 45 to 230) (1.5g), and stirring is carried out to prepare the composition for forming an intermediate layer.
The intermediate layer (thickness: 20 μm) was prepared by applying the obtained intermediate layer-forming composition to the release-treated surface of a release film obtained by peeling one surface of a polyethylene terephthalate film by silicone treatment, and drying the composition at 70 ℃ for 5 minutes.
< preparation of film-shaped adhesive >
A thermosetting adhesive composition containing polymer component (a) -1(100 parts by mass), epoxy resin (b1) -1(10 parts by mass), thermosetting agent (b2) -1(1.5 parts by mass), filler (d) -1(75 parts by mass), coupling agent (e) -1(0.5 parts by mass), crosslinking agent (f) -1(0.5 parts by mass), and antistatic agent (g) -1(5.6 parts by mass) was prepared.
Then, using a release film obtained by peeling one surface of a polyethylene terephthalate film by silicone treatment, the obtained adhesive composition was applied to the peeled surface, and heated and dried at 80 ℃ for 2 minutes, thereby producing a thermosetting film-like adhesive (thickness: 7 μm).
< production of sheet for semiconductor device production >
The exposed surface of the obtained adhesive layer on the side opposite to the side having the release film was bonded to one surface of the obtained substrate, thereby producing a first intermediate laminate with a release film (in other words, a support sheet with a release film).
The exposed surface of the obtained film-like adhesive on the side opposite to the side having the release film was bonded to the exposed surface of the obtained intermediate layer on the side opposite to the side having the release film, thereby producing a second intermediate laminate with a release film (a laminate of a release film, an intermediate layer, a film-like adhesive, and a release film).
Then, the second intermediate laminate with a release film was subjected to a press working using a dicing blade from the release film on the intermediate layer side to the film-shaped adhesive to remove unnecessary portions, thereby producing a second intermediate laminate with a release film in which the film-shaped adhesive (thickness 7 μm) having a circular planar shape (diameter 305mm), the intermediate layer (thickness 20 μm), and the release film were sequentially laminated in the thickness direction of the film-shaped adhesive-side release film.
Then, the release film was removed from the first intermediate laminate with the release film obtained above, and one surface of the adhesive layer was exposed.
Further, the circular release film was removed from the obtained second intermediate laminate with a release film, and one surface of the intermediate layer was exposed.
Then, the newly generated exposed surface of the adhesive layer in the first intermediate laminate is bonded to the newly generated exposed surface of the intermediate layer in the second intermediate laminate processed product. The base material and the adhesive agent layer (i.e., the support sheet) in the laminate thus obtained were subjected to press working using a dicing blade from the base material side so that the planar shape thereof was circular (diameter 305mm) and the shape thereof was concentric with the circular film-shaped adhesive agent and the intermediate layer, and unnecessary portions were removed.
Thus, a semiconductor device-manufacturing sheet with a release film of example 1 was obtained, which was composed of a substrate (thickness 110 μm), an adhesive layer (thickness 10 μm), an intermediate layer (thickness 20 μm), a film-like adhesive (thickness 7 μm), and a release film laminated in this order in the thickness direction.
[ evaluation of wafer for manufacturing semiconductor device ]
< measurement of surface resistivity of surface on intermediate layer side of film-shaped adhesive >
The release film of the obtained semiconductor device-manufacturing sheet with the release film was peeled off, and the entire exposed surface of the resulting film-like adhesive was bonded to the adhesive surface of an adhesive tape (PET 50(a) PL シン 8LK manufactured by linec Corporation) having a polyethylene terephthalate layer, and cut into 100mm × 100mm, thereby manufacturing a test piece. The test piece was subjected to humidity conditioning at 23 ℃ and 50% relative humidity for 24 hours, and then peeled off at the interface between the intermediate layer and the film-like adhesive, and the surface resistivity of the exposed surface of the film-like adhesive was measured using a digital electrometer (manufactured by ADVANTEST CORPORATION) by applying a voltage of 100V at 23 ℃ and 50% relative humidity.
< calculation of the ratio of silicon concentration on the film-like adhesive-side surface of the intermediate layer >
In the above-described process for producing a wafer for manufacturing a semiconductor device, the exposed surface of the intermediate layer at the stage before bonding to the adhesive layer is analyzed by XPS, the concentrations (atomic%) of carbon (C), oxygen (O), nitrogen (N), and silicon (Si) are measured, and the ratio (%) of the concentration of silicon to the total concentration of carbon, oxygen, nitrogen, and silicon is determined from the measured values.
The XPS analysis was carried out using an X-ray photoelectron spectroscopy apparatus ("Quantra SXM" manufactured by ULVAC, Inc.) under conditions of an irradiation angle of 45 °, an X-ray electron beam diameter of 20 μm φ, and a power of 4.5W. The results are shown in the column "proportion (%) of element concentration in the intermediate layer" in table 1 together with the proportion (%) of concentration of other elements.
< evaluation of the effect of suppressing the generation of chips at the time of cutting by the blade >
[ production of silicon chip set with film adhesive ]
The release film was removed from the semiconductor device-manufacturing sheet obtained as described above.
The back surface of a silicon wafer (diameter 300mm, thickness 75 μm) polished by dry polishing was bonded to the back surface (polished surface) of the silicon wafer with a film-like adhesive by a tape bonder ("adwire RAD 2500" manufactured by LINTEC Corporation) while heating the semiconductor device manufacturing sheet to 60 ℃. Thus, a laminate (a laminate obtained by laminating the laminate sheet, the film-like adhesive, and the silicon wafer in this order in the thickness direction) was obtained, which was composed of a substrate (thickness 110 μm), an adhesive agent layer (thickness 10 μm), an intermediate layer (thickness 20 μm), a film-like adhesive (thickness 7 μm), and a silicon wafer (thickness 75 μm) laminated in this order in the thickness direction.
Then, a region (the non-laminated region) in the vicinity of the peripheral portion of the first surface of the adhesive layer in the laminated body, on which the intermediate layer is not provided, is fixed to the ring frame for dicing.
Then, the silicon wafer was divided by dicing using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), and the film-like adhesive was also cut to obtain silicon chips having a size of 8mm × 8 mm. The cutting at this time was performed by: the rotation speed of the blade was 30000rpm, the moving speed of the blade was 30mm/s, and the blade was cut into the semiconductor device manufacturing sheet from the bonding surface of the silicon wafer with the film-like adhesive to the halfway region of the intermediate layer (i.e., the entire region in the thickness direction of the film-like adhesive and the region from the surface of the film-like adhesive side to the halfway region of the intermediate layer). As the blade, "Z05-SD 2000-D1-90 CC" manufactured by DISCO Corporation was used.
Thus, a silicon chip group with a film-like adhesive is obtained, which comprises silicon chips and a plurality of silicon chips with a film-like adhesive provided on the back surface thereof and having a film-like adhesive after cutting, wherein the silicon chips are aligned and fixed to the intermediate layer in the laminated sheet by the film-like adhesive.
[ evaluation of the Effect of suppressing the production of chips ]
The silicon chip group with the film-like pressure-sensitive adhesive obtained above was observed from above on the silicon chip side thereof using a digital microscope ("VH-Z100" manufactured by Keyence Corporation), and the presence or absence of the generation of cutting chips was confirmed. Then, the case where no chips were generated was determined as "a", and the case where even a small amount of chips were generated was determined as "B". The results are shown in Table 1.
< evaluation of cuttability of film-shaped adhesive during expansion >
[ production of silicon chip set with film adhesive ]
A silicon wafer having a circular planar shape with a diameter of 300mm and a thickness of 775 μm was used, and a back grinding tape ("Adwill E-3100 TN" manufactured by LINTEC Corporation) was attached to one surface thereof.
Then, laser light was irradiated using a laser irradiation apparatus ("DFL 73161" manufactured by DISCO Corporation) so as to be focused at a focal point set inside the silicon wafer, thereby forming a modified layer inside the silicon wafer. In this case, the focal point is set so that a plurality of silicon chips having a size of 8mm × 8mm can be obtained from the silicon wafer. The silicon wafer is irradiated with laser light from the other surface (surface to which the back grinding tape is not attached) side of the silicon wafer.
Then, the other surface of the silicon wafer was polished with a grinder to make the thickness of the silicon wafer 30 μm, and the silicon wafer was divided at the portion where the modified layer was formed by the force applied to the silicon wafer at the time of polishing, thereby producing a plurality of silicon chips. Thus, a silicon chip set in which a plurality of silicon chips are aligned and fixed to a back-grinding tape was obtained.
Then, one of the semiconductor device manufacturing sheets obtained as described above was heated to 60 ℃ while a film-like adhesive was attached to the other surface (in other words, a polished surface) of all the silicon chips (silicon chip groups) using a tape laminator ("Adwill RAD 2500" manufactured by LINTEC Corporation).
Then, a region (the non-laminated region) in the vicinity of the peripheral portion of the first surface of the adhesive layer in the semiconductor device manufacturing sheet to which the silicon chip group is attached, where the intermediate layer is not provided, is fixed to the ring frame for dicing.
Then, the back grinding tape was removed from the silicon chip group in the fixed state. Further, using a full-automatic die bonder ("DDS 2300" manufactured by DISCO Corporation), the semiconductor device manufacturing sheet was cooled while spreading it in a direction parallel to the surface thereof under an environment of 0 ℃, thereby cutting the film-like adhesive along the outer periphery of the silicon chip. At this time, the peripheral portion of the semiconductor device manufacturing sheet was fixed, and the entire region of the semiconductor device manufacturing sheet on which the intermediate layer and the film-like adhesive were laminated was pushed up to a height of only 15mm from the substrate side, thereby spreading the sheet.
Thus, a silicon chip group with a film-like pressure-sensitive adhesive was obtained, which was provided with a plurality of silicon chips with a film-like pressure-sensitive adhesive provided on the other surface (polished surface) of the silicon chip, and which was fixed in alignment to the intermediate layer.
Then, after the spread of the semiconductor device manufacturing sheet is once released, a laminated body (that is, the laminated sheet) formed by laminating the base material, the adhesive agent layer, and the intermediate layer is spread in a direction parallel to the first surface of the adhesive agent layer at normal temperature. Further, the peripheral portion of the semiconductor chip with the film-like adhesive not mounted thereon in the laminate sheet is heated while maintaining the spread state. Thereby, the peripheral portion is contracted, and the slit width between adjacent silicon chips in the laminated sheet is maintained at a predetermined value or more.
[ evaluation of cuttability of film-shaped adhesive ]
In the production of the silicon chip set with the film-like adhesive, the obtained silicon chip set with the film-like adhesive was observed from above the silicon chip side thereof using a digital microscope ("VH-Z100" manufactured by Keyence Corporation). In addition, it was confirmed that among a plurality of cutting lines of the film-like adhesive extending in one direction to be formed when the film-like adhesive was supposed to be normally cut by spreading of the semiconductor device manufacturing sheet and a plurality of cutting lines of the film-like adhesive extending in a direction orthogonal to the one direction, the number of cutting lines which were not actually formed and the number of cutting lines which were incompletely formed were each determined, and the cuttability of the film-like adhesive was evaluated based on the following evaluation criteria. The results are shown in Table 1.
(evaluation criteria)
A: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the incomplete film-shaped adhesive is 5 or less.
B: the total number of the cutting lines of the film-shaped adhesive which is not actually formed and the cutting lines of the incomplete film-shaped adhesive is more than 6.
< evaluation of pickup Property of silicon chip with film adhesive after expansion >
After the evaluation of the cuttability of the film-like adhesive described above, the silicon chip with the film-like adhesive was picked up from the intermediate layer in the laminated sheet under the conditions of a push-up height of 250 μm, a push-up speed of 5mm/s, and a push-up time of 500ms using a silicon chip set with the film-like adhesive and a die bonder ("PU 100" manufactured by fast Technology co., ltd.). In addition, a case where all the silicon chips with the film-like adhesive could be picked up normally was evaluated as "a", and a case where one or more silicon chips with the film-like adhesive could not be picked up normally was evaluated as "B". The results are shown in Table 1.
< measurement of T-shaped peel Strength between intermediate layer and film-shaped adhesive >
The release film was removed from the semiconductor device-manufacturing sheet obtained as described above.
The entire exposed surface of the film-like adhesive in the thus produced sheet for manufacturing a semiconductor device was bonded to the adhesive surface of an adhesive tape having a polyethylene terephthalate layer ("PET 50(a) PL シン 8 LK" manufactured by LINTEC Corporation), and the resulting laminate was cut into a size of 50mm × 100mm, thereby producing a test sheet.
The test piece was peeled in a T-shape by peeling a laminate of the substrate, the adhesive layer and the intermediate layer (that is, the laminate), and a laminate of the film-like adhesive and the adhesive tape according to JIS K6854-3, and the maximum value of the peel force (mN/50mm) measured at this time was defined as the T-peel strength. At this time, the peeling speed was set to 50 mm/min. The results are shown in Table 1.
< evaluation of reliability of semiconductor Package in chip/chip form >
(production of silicon chip set with film adhesive (1))
An adhesive surface of a back grinding tape ("ADWILL E-3125 KN" manufactured by LINTEC Corporation) was bonded to a mirror surface of a silicon wafer (8 inches, thickness of 720 μm) at normal temperature using a tape bonding apparatus ("RAD 3510" manufactured by LINTEC Corporation).
Then, the silicon wafer was made to be 75 μm thick by grinding (dry polishing process) it from the back surface side thereof using a grinder ("DGP 8760" manufactured by DISCO Corporation).
Then, the release film of the semiconductor device manufacturing sheet with the release film was peeled off, and the exposed surface of the film-like adhesive thus produced was bonded to a polished surface of a silicon wafer (8 inches, 75 μm thick) subjected to dry polishing using a laminating apparatus ("VA-400" manufactured by Taisei laser co. The lamination was carried out at 40 ℃ and lamination speed: 0.6m/min and 0.5 MPa. Thus, a laminated structure (1) was obtained in which a substrate (having a thickness of 110 μm), an adhesive layer (having a thickness of 10 μm), an intermediate layer (having a thickness of 20 μm), a film-like adhesive (having a thickness of 7 μm), a silicon wafer (having a thickness of 75 μm), and a back-grinding tape were laminated in this order in the thickness direction (laminated structure (1) in which the laminated sheet, the film-like adhesive, the silicon wafer, and the back-grinding tape were laminated in this order along the thicknesses thereof).
Then, the obtained laminated structure (1) was attached and fixed to a dicing ring frame, and the back grinding tape attached to the mirror surface side of the wafer was peeled off.
Then, the silicon wafer was divided under conditions of 50mm/s and 40,000rpm using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), while cutting the film-like adhesive, to thereby obtain a silicon wafer having a size of 8mm × 8 mm. The amount of cut at the time of cutting was set to 20 μm from the film-like adhesive layer side in the intermediate layer in the laminated sheet. Through the above steps, a silicon chip set (1) with a film-shaped adhesive for evaluating reliability of a semiconductor package is obtained, which comprises a plurality of silicon chips with a film-shaped adhesive provided on the back surface thereof and the film-shaped adhesive after cutting, wherein the silicon chips are aligned and fixed to the intermediate layer in the laminated sheet by the film-shaped adhesive.
(production of silicon chip set with adhesive layer (2))
A laminated structure (2) was obtained in which a substrate, an adhesive layer (thickness: 20 μm), a silicon wafer (thickness: 75 μm), and a back-grinding tape were laminated in this order in the thickness direction thereof, in the same manner as in the production of the laminated structure (1), except that the semiconductor device-producing sheet composed of a substrate, an adhesive layer (thickness: 20 μm), an intermediate layer, a film-like adhesive agent, and a release film was changed to a commercially available diced solid wafer (advil LE5729S, produced by LINTEC Corporation).
Then, the obtained laminated structure (2) was attached and fixed to a dicing ring frame, and the back grinding tape attached to the mirror surface side of the wafer was peeled off.
Then, using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), the silicon wafer was divided while cutting the adhesive layer under conditions of 50mm/s and 40,000rpm, thereby obtaining a silicon chip having a size of 8mm × 8 mm. The amount of the cut during dicing was set to 20 μm. Through the above steps, a silicon chip group (2) with an adhesive layer for reliability evaluation of a semiconductor package is obtained, wherein the silicon chip group is provided with a plurality of silicon chips with a film-shaped adhesive, which are provided on the back surface of the silicon chip and the adhesive layer after cutting, and the silicon chips are arranged in order by the adhesive layer and fixed on the intermediate layer in the laminated sheet.
(evaluation of reliability of semiconductor Package in chip/chip form)
As the substrate, a substrate ("LN 001E-001pcb (au) AUS 308" manufactured by inc., of ship ELECTRONICS) having a circuit pattern formed on a copper foil (having a thickness of 18 μm) of a copper clad laminate (MITSUBISHI GAS CHEMICAL COMPANY, inc., manufactured by HL832NX-a ") and a solder resist film (TAIYO INK mfg. co., ltd., manufactured by PSR-4000AUS 308") was used.
A silicon chip with an adhesive layer is picked up from a silicon chip group (2) with an adhesive layer for evaluating reliability of a semiconductor package. The silicon chip with the adhesive layer was laminated to the substrate via the adhesive layer at 120 ℃, 2.45N (250gf) and 0.5 sec, and the silicon chip was fixed to the substrate via the adhesive layer, thereby obtaining a laminate of the substrate and the silicon chip with the adhesive layer.
Then, the obtained laminate of the substrate and the silicon chip with the adhesive layer was heated at 160 ℃ for 1 hour using an oven.
Then, the laminate was taken out of the oven and cooled to normal temperature.
A silicon chip with a film-like adhesive is picked up from a silicon chip group (1) with a film-like adhesive for evaluating the reliability of a semiconductor package. The silicon chips with the film-like adhesive were pressure-bonded to the silicon chips of the laminate cooled to normal temperature under conditions of 120 ℃, 2.45N (250gf), 0.5 seconds, and heated at 160 ℃ for 1 hour using an oven. The laminate was then removed from the oven and cooled to ambient temperature. After sealing with a resin (KE-1100 AS3 manufactured by KYOCERA CHEMICAL CORPORATION) on the chip so AS to have a thickness of 400 μ M using a sealing device ("MPC-06M TriAl Press" manufactured by APIC YAMADA CORPORATION), the sealing resin was cured by heating at 175 ℃ for 5 hours.
Then, the sealed laminate was attached to a dicing tape ("Adwill D-510T" manufactured by LINTEC Corporation), cut into a size of 10mm × 10mm using a dicing apparatus ("DFD 6361" manufactured by DISCO Corporation), and a sealing resin film having a thickness of 1mm remained on the periphery of the side surface of the silicon chip having a size of 8mm × 8mm, to obtain a semiconductor package for reliability evaluation.
The semiconductor package in the form of a chip/chip obtained by further stacking semiconductor chips on the semiconductor chip was allowed to stand for 168 hours at a temperature of 85 ℃ and a relative humidity of 60% to absorb moisture (JEDEC Level 2). Then, the semiconductor package after moisture absorption was subjected to IR reflow 3 times using a desk top reflow oven ("STR-2010N 2M" manufactured by SENJU METAL induction co., ltd.) under conditions of a maximum temperature of 260 ℃ and a heating time of 1 minute. Then, the 9 semiconductor packages were evaluated for the presence of cracks in the semiconductor package of the chip/chip type obtained by further stacking semiconductor chips on the semiconductor chip and the presence of floating and peeling between the chips bonded with the film-shaped adhesive of the example, using an ultrasonic microscope ("D-9600" manufactured by SONOSCAN corporation), and the above evaluations were made for reliability evaluation. The results are shown in Table 1.
In table 1, for example, the expression "9/9" indicates that no semiconductor package in which floating, peeling, or cracking was observed was found in the evaluation of 9 semiconductor packages. The expression "8/9" indicates that no lifting, peeling, or cracks were observed in 8 semiconductor packages and no lifting, peeling, or package cracks were observed in 1 semiconductor package in the evaluation of 9 semiconductor packages.
Production and evaluation of wafer for producing semiconductor device
[ example 2]
A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that the antistatic agent in the adhesive composition was changed from 5.6 parts by mass (2.9 mass%) to 0.95 parts by mass (0.5 mass%) when the film-shaped adhesive was manufactured, and the siloxane compound was not added to the intermediate layer-forming composition when the intermediate layer was manufactured. The results are shown in Table 1. The "-" shown in the column of additives in Table 1 indicates that the additives were not used.
[ example 3]
A semiconductor device-manufacturing sheet was manufactured and evaluated in the same manner as in example 1, except that the siloxane compound was not added to the intermediate layer-forming composition during the preparation of the intermediate layer, and the content of the vinyl acetate-derived structural unit of the ethylene-vinyl acetate copolymer was changed from 25 mass% to 40 mass%. The results are shown in Table 1. The "-" shown in the column of additives in Table 1 indicates that the additives were not used.
[ example 4]
A semiconductor device-producing sheet was produced and evaluated in the same manner as in example 1, except that the siloxane compound was not added to the intermediate layer-forming composition during production of the intermediate layer, and the weight average molecular weight of the ethylene-vinyl acetate copolymer was changed from 30000 to 200000. The results are shown in Table 1. The "-" shown in the column of additives in Table 1 indicates that the additives were not used.
Comparative example 1
A semiconductor device-manufacturing sheet was produced and evaluated in the same manner as in example 1, except that no intermediate layer was provided. The results are shown in Table 2. The "-" shown in the additive column in Table 2 indicates that no intermediate layer was provided.
[ reference example 1]
A semiconductor device-producing sheet was produced and evaluated in the same manner as in example 1, except that the antistatic agent in the adhesive composition was changed from 5.6 parts by mass (2.9% by mass) to 7.9 parts by mass (4.0% by mass) in the production of the film-shaped adhesive, and the siloxane compound was not added to the intermediate layer-forming composition in the production of the intermediate layer. The results are shown in Table 2. The "-" shown in the column of additives in Table 2 indicates that the additives were not used.
[ reference example 2]
A semiconductor device-producing sheet was produced and evaluated in the same manner as in example 1, except that the antistatic agent was not added to the adhesive composition when the film-shaped adhesive was produced, and the siloxane-based compound was not added to the intermediate layer-forming composition when the intermediate layer was produced. The results are shown in Table 2. The "-" shown in the column of additives in Table 2 indicates that the additives were not used.
[ Table 1]
Figure BDA0003621497860000711
[ Table 2]
Figure BDA0003621497860000721
As is clear from the above results, in examples 1 to 4, the generation of chips was suppressed during dicing, the cutting failure of the film-like adhesive was suppressed during spreading, and the semiconductor wafer had excellent suitability for dividing.
In examples 1 to 4, the surface resistivity of the surface on the middle layer side of the film-like adhesive was 1X 1013Ω or less, and it is expected to prevent generation of static electricity or damage to a circuit due to electrification of a semiconductor wafer or the like caused by generation of static electricity.
In examples 1 to 3, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as a main component in the intermediate layer in the sheet for manufacturing a semiconductor device was 30000. In example 4, the weight average molecular weight of the ethylene-vinyl acetate copolymer was 200000.
In examples 1 to 4, the content of the ethylene-vinyl acetate copolymer in the intermediate layer was 90 mass% or more with respect to the total mass of the intermediate layer, and the content of the siloxane compound was 10 mass% or less with respect to the total mass of the intermediate layer.
In example 1, the silicon chip with the film-like adhesive after spreading was further excellent in pickup properties.
In example 1, the T-peel strength between the intermediate layer and the film-like adhesive was 100mN/50mm or less, which was moderately low, and the silicon concentration ratio of the intermediate layer was 9%, which was moderately high. These evaluation results were in agreement with the evaluation results of the above-described pickup property of the silicon chip with a film-like pressure-sensitive adhesive.
In examples 2 to 4, the intermediate layer in the sheet for producing a semiconductor device did not contain the siloxane compound.
In examples 1 to 4, no nitrogen was detected when the exposed surface of the intermediate layer was analyzed by XPS.
In examples 1 to 4, the semiconductor packages of chip/chip type in which semiconductor chips were further stacked on the semiconductor chips were excellent in reliability.
In contrast, in comparative example 1, the generation of chips was not suppressed during dicing, and the semiconductor wafer had poor suitability for dicing.
In reference examples 1 to 2, the weight average molecular weight of the ethylene-vinyl acetate copolymer contained as a main component in the intermediate layer in the sheet for manufacturing a semiconductor device was 30000.
In reference example 1, the surface resistivity is small, and it is expected that it can prevent the generation of static electricity or the damage of a circuit due to the electrification of a semiconductor wafer or the like caused by the generation of static electricity. However, in reference example 1, the content of the antistatic agent is more than 3 mass% with respect to the total mass of the film-shaped adhesive, and as a result, the adhesion performance of the film-shaped adhesive is impaired, and the reliability of the chip/chip type semiconductor package is poor. In reference example 2, the surface resistivity was large, and static electricity was likely to be generated.
In reference examples 1 to 2, no nitrogen was detected even when the exposed surface of the intermediate layer was subjected to XPS analysis.
Industrial applicability
The invention can be used for manufacturing semiconductor devices.
Description of the reference numerals
101: a semiconductor device manufacturing sheet; 11: a substrate; 12: an adhesive layer; 13: an intermediate layer; 13 a: a first side of the intermediate layer; 14: a film-like adhesive.

Claims (7)

1. A sheet for manufacturing a semiconductor device, comprising a base material, an adhesive layer, an intermediate layer and a film-like adhesive,
the sheet for manufacturing a semiconductor device is formed by laminating the adhesive layer, the intermediate layer, and the film-like adhesive in this order on the substrate,
the film-shaped adhesive contains an antistatic agent, the content of the antistatic agent is 3 mass% or less relative to the total mass of the film-shaped adhesive,
the intermediate layer contains a non-silicone resin having a weight average molecular weight of 100000 or less as a main component,
the surface resistivity of the surface of the film-like adhesive on the intermediate layer side is 1X 1013Omega is less than or equal to.
2. The sheet for manufacturing a semiconductor device according to claim 1, wherein a ratio of a concentration of silicon to a total concentration of carbon, oxygen, nitrogen and silicon is 1 to 20% when a surface of the intermediate layer on the film-like binder side is analyzed by X-ray photoelectron spectroscopy.
3. The sheet for manufacturing a semiconductor device according to claim 1 or 2, wherein the intermediate layer contains an ethylene-vinyl acetate copolymer or a polyolefin as the non-silicon resin.
4. The semiconductor device-manufacturing sheet according to claim 3,
the intermediate layer contains an ethylene-vinyl acetate copolymer as the non-silicone resin,
in the ethylene-vinyl acetate copolymer, the proportion of the mass of the structural unit derived from vinyl acetate to the total mass of all the structural units is 10 to 40% by mass.
5. The semiconductor device-manufacturing sheet according to claim 4,
the intermediate layer contains an ethylene-vinyl acetate copolymer and a silicone compound as the non-silicone resin,
in the intermediate layer, the content of the ethylene-vinyl acetate copolymer is 90-99.99% by mass relative to the total mass of the intermediate layer,
in the intermediate layer, the ratio of the content of the siloxane compound to the total mass of the intermediate layer is 0.01-10 mass%.
6. A method for manufacturing a semiconductor chip with a film-like adhesive, comprising:
a step of attaching the back surface of a semiconductor wafer to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet according to any one of claims 1 to 5 to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive and the semiconductor wafer are laminated in this order;
cutting the film-like adhesive while the semiconductor wafer is being diced to obtain semiconductor chips with the film-like adhesive; and
and a step of pulling the semiconductor chip with the film-like adhesive off the base material, the adhesive layer, and the intermediate layer to pick up the semiconductor chip.
7. A method for manufacturing a semiconductor chip with a film-like adhesive, comprising:
a step of attaching the back surfaces of the semiconductor chip groups in which the plurality of semiconductor chips are aligned to the exposed surface of the film-like adhesive of the semiconductor device manufacturing sheet according to any one of claims 1 to 5 to obtain a laminate in which the base material, the adhesive layer, the intermediate layer, the film-like adhesive and the semiconductor chip groups are stacked in this order;
cutting the film-shaped adhesive to obtain a semiconductor chip with the film-shaped adhesive; and
and a step of pulling the semiconductor chip with the film-like adhesive off the base material, the adhesive layer, and the intermediate layer to pick up the semiconductor chip.
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