CN112930584A - Method for manufacturing semiconductor device and adhesive film for processing semiconductor wafer - Google Patents

Method for manufacturing semiconductor device and adhesive film for processing semiconductor wafer Download PDF

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Publication number
CN112930584A
CN112930584A CN201980070581.7A CN201980070581A CN112930584A CN 112930584 A CN112930584 A CN 112930584A CN 201980070581 A CN201980070581 A CN 201980070581A CN 112930584 A CN112930584 A CN 112930584A
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adhesive layer
semiconductor wafer
hydroxy
meth
pressure
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CN201980070581.7A
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佐藤慎
茶花幸一
谷口徹弥
林出明子
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Resonac Holdings Corp
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Showa Denko KK
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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    • 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
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    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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    • 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
    • H01L2221/68377—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 with parts of the auxiliary support remaining in the finished device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
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    • H01—ELECTRIC ELEMENTS
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    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
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    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
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    • H01L2224/81—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a bump connector
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    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
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    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/13—Discrete devices, e.g. 3 terminal devices
    • H01L2924/1304—Transistor
    • H01L2924/1306—Field-effect transistor [FET]
    • H01L2924/13081—Multigate devices
    • H01L2924/13082—Tetrode transistor

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  • Engineering & Computer Science (AREA)
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  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)

Abstract

A method for manufacturing a semiconductor device, comprising: preparing a semiconductor wafer having a plurality of electrodes on one main surface thereof, and attaching a semiconductor wafer processing adhesive film, which includes a back surface polishing tape including a base material and a pressure-sensitive adhesive layer, and an adhesive layer formed on the pressure-sensitive adhesive layer, to a side of the semiconductor wafer on which the electrodes are provided, to obtain a laminate; grinding the semiconductor wafer to reduce the thickness of the semiconductor wafer; dicing the semiconductor wafer and the adhesive layer into individual semiconductor chips with the adhesive layer, the semiconductor chips being thinned; and a step of electrically connecting the electrode of the semiconductor chip with the adhesive layer to the electrode of another semiconductor chip or a printed circuit board, wherein the thickness of the back grinding tape is 75 to 300 [ mu ] m, and the thickness of the pressure-sensitive adhesive layer is 3 times or more the thickness of the adhesive layer.

Description

Method for manufacturing semiconductor device and adhesive film for processing semiconductor wafer
Technical Field
The present invention relates to a method for manufacturing a semiconductor device and an adhesive film for processing a semiconductor wafer.
Background
In recent years, with the miniaturization and thinning of electronic devices, the density of circuits formed in circuit components has increased, and the spacing between adjacent electrodes and the width of the electrodes tend to be extremely narrow. Thus, demands for thinning and downsizing of a semiconductor package (page) have been increasing. Therefore, as a mounting method of a semiconductor chip (chip), a flip chip (flip chip) connection method in which bump electrodes called bumps (bumps) are formed on chip electrodes and substrate electrodes and the chip electrodes are directly connected via the bumps has been attracting attention, instead of a conventional wire bonding method in which connection is performed using metal wires (wires).
As flip chip connection methods, a method using a solder bump, a method using a gold bump and a conductive adhesive, a thermocompression bonding method, an ultrasonic method, and the like are known. In these modes, there is a problem that thermal stress due to the difference in thermal expansion between the chip and the substrate is concentrated in the connection portion, and connection reliability is lowered. In order to prevent such a decrease in connection reliability, an underfill (underfill) filling a gap between the chip and the substrate is generally formed with a resin. Since the thermal stress is relaxed by being dispersed in the underfill, the connection reliability can be improved.
In general, as a method of forming the underfill agent, a method of connecting the semiconductor chip and the substrate with solder or the like and then injecting a liquid sealing resin into the gap by capillary action is employed. In order to facilitate metal bonding by reducing and removing an oxide film on the solder surface when connecting a chip and a substrate, a flux (flux) containing rosin, an organic acid, or the like is used, but if the flux remains, bubbles called voids (void) are generated when a liquid resin is injected, or corrosion of wiring occurs due to an acid component, and the connection reliability is lowered, and thus a step of cleaning the residue is necessary. However, as the gap between the semiconductor chip and the substrate becomes narrower with the progress of fine connection, cleaning of the flux residue may become difficult. Further, it takes a long time to inject the liquid resin into the narrow gap between the semiconductor chip and the substrate, and there is a problem that productivity is lowered.
In order to solve the problem of the liquid sealing resin, a connection method called a pre-supply method has been proposed in which a sealing resin having a property of reducing and removing an oxide film on a solder surface (hereinafter referred to as flux activity) is used, the sealing resin is supplied to a substrate, and then a gap between a semiconductor chip and the substrate is sealed and filled with the resin while the semiconductor chip and the substrate are connected, thereby eliminating cleaning of flux residue. Further, a sealing resin corresponding to this connection method is being developed.
In addition, with the demand for further thinning of semiconductor devices, so-called back grinding (back grind) is performed to grind the back surface of a semiconductor wafer in order to make the semiconductor wafer thinner, and the manufacturing process of the semiconductor device becomes complicated. Therefore, as a method suitable for simplification of the process, a resin having both a function of holding a semiconductor wafer at the time of back grinding and an underfill function has been proposed (see patent documents 1 to 3).
Prior art documents
Patent document
Patent document 1: japanese patent laid-open No. 2001-332520
Patent document 2: japanese patent laid-open publication No. 2005-028734
Patent document 3: japanese patent laid-open No. 2009-239138
Disclosure of Invention
Technical problem to be solved by the invention
However, in the pre-feeding method, after the semiconductor chip is mounted, resin called fillet (fillet) is likely to overflow to the outside of the chip. When the fillet is large, it becomes difficult to mount the adjacent chips, and therefore, it is necessary to suppress the fillet. As a method of suppressing the fillet, for example, it is considered to make the thickness of a film-like resin (adhesive layer) supplied as a sealing resin the same as or smaller than the height of the bump.
However, since bumps and irregularities such as scribe lines (scribes lines) which are the standard in dicing processing are formed on a semiconductor wafer, there is a problem that voids are likely to remain when a thin film-like resin is laminated. When a void remains in the bump periphery, the void is likely to remain even after mounting. Further, since the voids expand during the reliability test, there is a problem that cracks are likely to occur in the resin for reinforcing the connection portion, or the connection portion is likely to be broken. Further, when a void remains in the scribe line, the void becomes a starting point during dicing and the film-like resin is likely to peel off from the wafer.
As a method for suppressing the voids, it is conceivable to improve the following property of the film-like resin to the irregularities on the semiconductor wafer. In order to improve the follow-up property, it is conceivable to use a resin having high fluidity as the film-like resin, to increase the lamination temperature, or the like. However, the former method has a problem that a fillet is likely to be generated although a void can be suppressed. In the latter case, the amount of shrinkage of the base material of the back side polishing tape after lamination is increased by heat applied during lamination. Therefore, the wafer after back grinding cannot suppress shrinkage of the base material, and the wafer has a problem of large warpage.
The present invention has been made in view of the problems of the conventional techniques described above, and an object thereof is to provide a method for manufacturing a semiconductor device and an adhesive film for processing a semiconductor wafer, which can suppress the generation of voids when an adhesive layer is laminated without adversely affecting fillet and wafer warpage.
Means for solving the technical problem
In order to achieve the above object, the present invention provides a method for manufacturing a semiconductor device, comprising: preparing a semiconductor wafer having a plurality of electrodes on one main surface thereof, and attaching a semiconductor wafer processing adhesive film including a base material, a back-grinding tape including a pressure-sensitive adhesive layer formed on the base material, and an adhesive layer formed on the pressure-sensitive adhesive layer, to a side of the semiconductor wafer on which the electrodes are provided, from the adhesive layer side, to obtain a laminate; grinding a side of the semiconductor wafer opposite to a side on which the electrode is provided to reduce a thickness of the semiconductor wafer; dicing the semiconductor wafer having the reduced thickness and the adhesive layer into individual semiconductor chips having the adhesive layer; and a step of electrically connecting the electrode of the semiconductor chip with the adhesive layer to an electrode of another semiconductor chip or a printed circuit board, wherein the thickness of the back grinding tape is 75 to 300 μm, and the thickness of the pressure-sensitive adhesive layer is 3 times or more the thickness of the adhesive layer.
According to the above production method, the thickness of the back-grinding tape composed of the base material and the pressure-sensitive adhesive layer is set to 75 μm to 300 μm, and the thickness of the pressure-sensitive adhesive layer is set to 3 times or more the thickness of the adhesive layer, whereby the occurrence of voids at the time of laminating the adhesive layer can be suppressed even when the adhesive layer is made thin. Here, the back-grinding tape and the pressure-sensitive adhesive layer thereof in the adhesive film for processing a semiconductor wafer need only be capable of holding the semiconductor wafer during back grinding, and since the back-grinding tape and the pressure-sensitive adhesive layer thereof do not directly contact the semiconductor wafer, the relationship between the thickness of the back-grinding tape and the pressure-sensitive adhesive layer thereof and the gap has not been studied in the past. However, the present inventors have made extensive studies and as a result, have found that the thickness of the back grinding tape and the pressure-sensitive adhesive layer thereof is adjusted to satisfy the above conditions, so that the entire back grinding tape can be made low in elastic modulus, and the ability of the adhesive film for processing a semiconductor wafer to follow the irregularities on the semiconductor wafer can be improved. This can suppress the generation of voids when the adhesive layer is laminated without increasing the fluidity of the adhesive layer or the laminating temperature. In addition, in the above manufacturing method, since it is not necessary to change the composition of the adhesive layer and the lamination conditions in order to suppress the generation of voids, the fillet and the wafer warpage are not adversely affected. Further, it was confirmed that the above-mentioned production method does not adversely affect the back-grinding property.
In the above production method, the back grinding tape may have an elastic modulus at 35 ℃ of 1.5GPa or less. In this case, the ability of the adhesive film for processing a semiconductor wafer to follow the irregularities on the semiconductor wafer can be further improved, and the occurrence of voids at the time of laminating the adhesive layer can be further suppressed.
In the above production method, the substrate may be a polyethylene terephthalate film. In this case, the deformation of the base material due to the tension during conveyance in the laminating device can be further suppressed, and the cutting property when the adhesive film for semiconductor wafer processing is precut to a wafer size can be improved, and the generation of burrs can be suppressed.
In the manufacturing method, an adhesive force between the pressure-sensitive adhesive layer and the adhesive layer may be lower than an adhesive force between the adhesive layer and the semiconductor wafer. In this case, after the back-grinding of the semiconductor wafer, only the back-grinding tape can be easily peeled off with the adhesive layer remaining on the semiconductor wafer.
In the manufacturing method, the thickness of the adhesive layer may be smaller than the height of the electrode of the semiconductor wafer. The manufacturing method of the present invention is preferable when the thickness of the adhesive layer is reduced to be smaller than the height of the electrode of the semiconductor wafer. Even when the adhesive layer is made thin in this way, generation of voids can be suppressed when laminating the adhesive layer.
In the above manufacturing method, the semiconductor wafer may have a groove in a main surface having the electrode. The manufacturing method of the present invention is preferable when a semiconductor wafer having a groove such as a scribe line on the surface is used. Even in the case of using such a semiconductor wafer having a groove, generation of voids at the time of lamination of the adhesive layer can be suppressed.
Further, the present invention provides an adhesive film for processing a semiconductor wafer, comprising: the back grinding belt comprises a base material and a pressure-sensitive adhesive layer formed on the base material; and an adhesive layer formed on the pressure-sensitive adhesive layer, wherein the thickness of the back grinding tape is 75-300 μm, and the thickness of the pressure-sensitive adhesive layer is more than 3 times of the thickness of the adhesive layer.
According to the adhesive film, the thickness of the back-grinding tape composed of the base material and the pressure-sensitive adhesive layer is set to 75 μm to 300 μm, and the thickness of the pressure-sensitive adhesive layer is set to 3 times or more the thickness of the adhesive layer, so that even when the adhesive layer is made thin, the generation of voids at the time of laminating the adhesive layer can be suppressed.
In the adhesive film, the back surface polishing tape may have an elastic modulus of 1.5GPa or less at 35 ℃. Also, the substrate may be a polyethylene terephthalate film.
Effects of the invention
According to the present invention, it is possible to provide a method for manufacturing a semiconductor device and an adhesive film for processing a semiconductor wafer, which can suppress the generation of voids when an adhesive layer is laminated without adversely affecting fillet and wafer warpage.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of an adhesive film for semiconductor wafer processing of the present invention.
Fig. 2 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor device of the present invention.
Fig. 3 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor device of the present invention.
Fig. 4 is a schematic cross-sectional view for explaining one embodiment of a method for manufacturing a semiconductor device of the present invention.
Fig. 5 is a schematic cross-sectional view showing one embodiment of a semiconductor device of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings as appropriate. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and redundant description thereof is omitted. Unless otherwise specified, the positional relationship such as vertical, horizontal, and the like is based on the positional relationship shown in the drawings. The dimensional ratios in the drawings are not limited to the illustrated ratios.
In the present specification, a numerical range represented by "to" means a range in which numerical values before and after "to" are included as a minimum value and a maximum value, respectively. In the numerical ranges recited in the present specification, the upper limit or the lower limit of the numerical range in one stage may be arbitrarily combined with the upper limit or the lower limit of the numerical range in another stage. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. The term "a" or "B" may include both a and B, as long as both a and B are included. The materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified. In the present specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid corresponding thereto.
One embodiment of a method for manufacturing a semiconductor device according to the present invention includes: preparing a semiconductor wafer having a plurality of electrodes on one main surface thereof, and attaching a semiconductor wafer processing adhesive film including a base material, a back-grinding tape including a pressure-sensitive adhesive layer formed on the base material, and an adhesive layer formed on the pressure-sensitive adhesive layer, to a side of the semiconductor wafer on which the electrodes are provided, from the adhesive layer side, to obtain a laminate; grinding a side of the semiconductor wafer opposite to a side on which the electrode is provided to reduce a thickness of the semiconductor wafer; dicing the semiconductor wafer and the adhesive layer into individual semiconductor chips with adhesive layers, the semiconductor chips being thinned; and a step of electrically connecting the electrode of the semiconductor chip with the adhesive layer to an electrode of another semiconductor chip or a printed circuit board.
Fig. 1 is a schematic cross-sectional view showing one embodiment of an adhesive film for semiconductor wafer processing of the present invention. The adhesive film 10 for semiconductor wafer processing shown in fig. 1 includes a support substrate 1, a film-like adhesive (adhesive layer) 2, and a back-grinding tape 5. The back grinding tape 5 includes a pressure-sensitive adhesive layer 3 and a base material 4. In the adhesive film 10 of the present embodiment, the thickness of the back surface polishing tape 5 is 75 μm to 300 μm, and the thickness of the pressure-sensitive adhesive layer 3 is 3 times or more the thickness of the adhesive layer 2. The adhesive film 10 of the present embodiment is a film that can serve both the purpose of back grinding and the purpose of connecting circuit components, and the adhesive layer 2 is attached to the main surface of the semiconductor wafer on the side where the electrodes are provided.
First, the adhesive composition constituting the adhesive layer 2 will be described.
The adhesive composition of the present embodiment contains, for example, an epoxy resin (hereinafter, referred to as "component (a)" in some cases), a curing agent (hereinafter, referred to as "component (b)" in some cases), and a flux (hereinafter, referred to as "component (c)" in some cases).
The adhesive composition of the present embodiment may contain a polymer component having a weight average molecular weight of 10000 or more (hereinafter, referred to as "component (d)", as occasion demands), as necessary. The adhesive composition of the present embodiment may contain a filler (hereinafter, referred to as "component (e)", as occasion demands).
Hereinafter, each component constituting the adhesive composition of the present embodiment will be described.
(a) The components: epoxy resin
The epoxy resin may be used without particular limitation if it has two or more epoxy groups in the molecule. As the component (a), for example, there can be used: bisphenol a type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, and various polyfunctional epoxy resins. These can be used alone or as a mixture of two or more.
From the viewpoint of suppressing the generation of volatile components due to the decomposition of the component (a) at the time of connection at a high temperature, it is preferable to use an epoxy resin having a thermal weight loss rate of 5% or less at 250 ℃ when the temperature at the time of connection is 250 ℃, and to use an epoxy resin having a thermal weight loss rate of 5% or less at 300 ℃ when the temperature at the time of connection is 300 ℃.
The content of the component (a) is, for example, 5 to 75% by mass, preferably 10 to 50% by mass, and more preferably 15 to 35% by mass, based on the total amount of the binder composition (excluding the solvent).
(b) The components: curing agent
Examples of the component (b) include: phenol resin curing agents, acid anhydride curing agents, amine curing agents, imidazole curing agents and phosphine curing agents. When the component (b) contains a phenolic hydroxyl group, an acid anhydride, an amine or an imidazole, the solder activity of suppressing the generation of an oxide film in the connecting portion is exhibited, and the connection reliability and the insulation reliability can be improved. Hereinafter, each curing agent will be described.
(i) Phenol resin curing agent
The phenolic resin curing agent is not particularly limited as long as it has two or more phenolic hydroxyl groups in the molecule, and for example, the following can be used: phenol novolac resins, cresol novolac resins, phenol aralkyl resins, cresol naphthol formaldehyde condensation polymers, triphenylmethane type polyfunctional phenol resins, and various polyfunctional phenol resins. These can be used alone or as a mixture of two or more.
From the viewpoint of good curability, adhesiveness, and storage stability, the equivalent ratio (molar ratio of phenolic hydroxyl groups to epoxy groups) of the phenolic resin curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and still more preferably 0.5 to 1.0. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesive force tends to be improved, and when it is 1.5 or less, unreacted phenolic hydroxyl groups do not remain excessively, water absorption is suppressed to be low, and insulation reliability tends to be improved.
(ii) Acid anhydride curing agent
Examples of the acid anhydride curing agent include: methylcyclohexane tetracarboxylic dianhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, and ethylene glycol bistrimellitic anhydride ester. These can be used alone or as a mixture of two or more.
From the viewpoint of good curability, adhesiveness, and storage stability, the equivalent ratio (acid anhydride group/epoxy group, molar ratio) of the acid anhydride-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and further preferably 0.5 to 1.0. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesive force tends to be improved, and when it is 1.5 or less, unreacted acid anhydride does not excessively remain, water absorption is suppressed to be low, and insulation reliability tends to be improved.
(iii) Amine-based curing agent
As the amine-based curing agent, dicyanodiamine can be used, for example.
The equivalent ratio (amine/epoxy group, molar ratio) of the amine-based curing agent to the component (a) is preferably 0.3 to 1.5, more preferably 0.4 to 1.0, and even more preferably 0.5 to 1.0, from the viewpoint of good curability, adhesion, and storage stability. When the equivalent ratio is 0.3 or more, curability tends to be improved and adhesion tends to be improved, and when it is 1.5 or less, insulation reliability tends to be improved without excessive residual unreacted amine.
(iv) Imidazole curing agent
Examples of the imidazole-based curing agent include: 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 '-undecylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 '-ethyl-4' -methylimidazole Oxazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and imidazoles. Among these, from the viewpoint of excellent curability, storage stability and connection reliability, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine isocyanurate, and the addition product of ethyl-s-triazine isocyanuric acid, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. These can be used alone or in combination of two or more. Further, a latent curing agent obtained by microencapsulating these components may be used.
The content of the imidazole-based curing agent is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the component (a). When the content of the imidazole curing agent is 0.1 parts by mass or more, curability tends to be improved, and when it is 20 parts by mass or less, the adhesive composition tends not to be cured before the metal joint is formed, and poor connection tends not to occur.
(v) Phosphine curing agent
Examples of the phosphine-based curing agent include: triphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis (4-methylphenyl) borate and tetraphenylphosphonium (4-fluorophenyl) borate.
The content of the phosphine-based curing agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (a). When the content of the phosphine-based curing agent is 0.1 parts by mass or more, curability tends to be improved, and when it is 10 parts by mass or less, the adhesive composition tends not to be cured before the metal joint is formed, and poor connection tends not to occur.
The phenol resin-based curing agent, the acid anhydride-based curing agent and the amine-based curing agent may be used singly or as a mixture of two or more kinds. The imidazole-based curing agent and the phosphine-based curing agent may be used alone or in combination with a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent.
The component (b) is preferably a curing agent selected from the group consisting of phenol resin curing agents, amine curing agents, imidazole curing agents and phosphine curing agents, from the viewpoint of further improving storage stability and preventing decomposition or deterioration due to moisture absorption. The component (b) is more preferably a curing agent selected from the group consisting of a phenol resin curing agent, an amine curing agent and an imidazole curing agent, from the viewpoint of ease of adjustment of the curing rate and the viewpoint of achieving short-time connection for the purpose of improving productivity by rapid curing.
When the binder composition contains a phenol resin-based curing agent, an acid anhydride-based curing agent, or an amine-based curing agent as the component (b), the flux activity is exhibited with an oxide film removed, and the connection reliability can be further improved.
(c) The components: welding flux
(c) The component (b) is a compound having flux activity (activity of removing oxides, impurities, etc.). Examples of the component (c) include nitrogen-containing compounds (imidazoles, amines, and the like, except for the compounds contained in the component (b)), carboxylic acids, phenols, alcohols, and the like, which have an unshared electron pair. In addition, carboxylic acids exhibit more strongly flux activity than alcohols, and are likely to improve connectivity. (c) The components can be used singly or in combination of two or more.
(c) The component (b) may be a compound having a group represented by the following formula (1) (hereinafter, referred to as "flux compound" as the case may be).
Figure BDA0003037482860000101
In the formula (1), R1Represents an electron donating group.
Examples of the electron donating group include: alkyl, hydroxy, amino, alkoxy and alkylamino. The electron donating group is preferably a group which does not easily react with other components (for example, the epoxy resin of the component (a)), and specifically, is preferably an alkyl group, a hydroxyl group, or an alkoxy group, and more preferably an alkyl group.
When the electron donating property of the electron donating group is enhanced, the effect of suppressing the decomposition of the ester bond tends to be obtained easily. Further, when the steric hindrance of the electron-donating group is large, the effect of suppressing the reaction between the carboxyl group and the epoxy resin is easily obtained. The electron-donating group preferably has electron-donating properties and steric hindrance in a good balance.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The larger the number of carbon atoms of the alkyl group, the larger the electron donating property and the steric hindrance tend to be. Since the alkyl group having a carbon number within the above range is excellent in the balance between electron donating properties and steric hindrance, reflow resistance and connection reliability can be improved by the alkyl group.
The alkyl group may be linear or branched, and is preferably linear. When the alkyl group is linear, the number of carbon atoms of the alkyl group is preferably equal to or less than the number of carbon atoms of the main chain of the flux compound from the viewpoint of the balance between electron donating property and steric hindrance. For example, when the flux compound is a compound represented by the following formula (2) and the electron donating group is a linear alkyl group, the number of carbon atoms of the alkyl group is preferably equal to or less than the number of carbon atoms (n +1) of the main chain of the flux compound.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. The larger the number of carbon atoms of the alkoxy group, the larger the electron donating property and the steric hindrance tend to be. Since the alkoxy group having a carbon number within the above range is excellent in the balance between electron donating properties and steric hindrance, reflow resistance and connection reliability can be improved by the alkoxy group.
The alkyl moiety of the alkoxy group may be linear or branched, and is preferably linear. When the alkoxy group is linear, the number of carbon atoms of the alkoxy group is preferably equal to or less than the number of carbon atoms of the main chain of the flux compound from the viewpoint of the balance between electron donating properties and steric hindrance. For example, when the flux compound is a compound represented by the following formula (2) and the electron donating group is a linear alkoxy group, the number of carbon atoms of the alkoxy group is preferably equal to or less than the number of carbon atoms (n +1) of the main chain of the flux compound.
Examples of the alkylamino group include a monoalkylamino group and a dialkylamino group. The monoalkylamino group is preferably a monoalkylamino group having 1 to 10 carbon atoms, and more preferably a monoalkylamino group having 1 to 5 carbon atoms. The alkyl moiety of the monoalkylamino group may be linear or branched, and is preferably linear.
The dialkylamino group is preferably a dialkylamino group having 2 to 20 carbon atoms, and more preferably a dialkylamino group having 2 to 10 carbon atoms. The alkyl moiety of the dialkylamino group may be linear or branched, and is preferably linear.
The flux compound is preferably a compound having two carboxyl groups (dicarboxylic acid). The compound having two carboxyl groups is less volatile even at high temperature during the connection than the compound having one carboxyl group (monocarboxylic acid), and generation of voids can be further suppressed. Further, when the compound having two carboxyl groups is used, the viscosity increase of the adhesive composition during storage, connection work, and the like can be further suppressed as compared with the case of using the compound having three or more carboxyl groups, and the connection reliability of the semiconductor device can be further improved.
As the flux compound, a compound represented by the following formula (2) can be preferably used. According to the compound represented by the following formula (2), the reflow resistance and the connection reliability of the semiconductor device can be further improved.
Figure BDA0003037482860000111
In the formula (2), R1Represents an electron donating group, R2Represents a hydrogen atom or an electron donating group, n represents an integer of 0 or 1 or more, and R is present in plural2May be the same or different from each other.
N in formula (2) is preferably 1 or more. When n is 1 or more, the flux compound is less volatile even at high temperature during connection than when n is 0, and generation of voids can be further suppressed. In formula (2), n is preferably 15 or less, more preferably 11 or less, and may be 6 or less or 4 or less. When n is 15 or less, further excellent connection reliability can be obtained.
Further, the flux compound is more preferably a compound represented by the following formula (3). According to the compound represented by the following formula (3), the reflow resistance and the connection reliability of the semiconductor device can be further improved.
Figure BDA0003037482860000112
In the formula (3), R1Represents an electron donating group, R2Represents a hydrogen atom or an electron donating group, and m represents an integer of 0 or 1 or more.
M in formula (3) is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. When m is 10 or less, further excellent connection reliability can be obtained.
In the formula (3), R2May be a hydrogen atom or an electron donating group. If R is2Hydrogen atoms tend to have a low melting point, and may further improve the connection reliability of the semiconductor device. And, if R1And R2Different electron donating groups than R1And R2When the electron donating groups are the same, the melting point tends to be low, and the connection reliability of the semiconductor device may be further improved.
In the compound represented by the formula (3), R is2Compounds which are hydrogen atoms include: methylsuccinic acid, 2-methylpentanediAcids, 2-methyladipic acid, 2-methylheptanoic acid, 2-methylsuberic acid, and the like. These compounds can further improve the connection reliability of the semiconductor device. Among these compounds, methylsuccinic acid and 2-methylglutaric acid are particularly preferable.
In addition, in the formula (3), if R1And R2The same electron-donating group tends to have a symmetrical structure and a high melting point, but even in this case, the effects of improving the reflow resistance and the connection reliability can be sufficiently obtained. Especially when the melting point is sufficiently low at 150 ℃ or lower, even if R is1And R2Are the same radicals, and R is also obtainable1And R2The same degree of connection reliability is the case for different groups.
As the flux compound, for example, a compound in which an electron donating group is substituted at the 2-position of a dicarboxylic acid selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid can be used.
The melting point of the flux compound is preferably 150 ℃ or lower, more preferably 140 ℃ or lower, and further preferably 130 ℃ or lower. Such a flux composition easily exhibits flux activity sufficiently before a curing reaction of the epoxy resin and the curing agent occurs. Therefore, the adhesive composition containing such a flux compound can realize a semiconductor device having further excellent connection reliability. The melting point of the flux compound is preferably 25 ℃ or higher, and more preferably 50 ℃ or higher. Also, the flux composition is preferably solid at room temperature (25 ℃).
The melting point of the flux composition can be measured using a conventional melting point measuring apparatus. It is required to reduce temperature variation in a sample by pulverizing the sample for measuring the melting point into fine powder and using a trace amount. As a sample container, a capillary tube having one end closed is often used, but depending on the measurement apparatus, the sample container may be sandwiched between two pieces of cover glass for a microscope. Further, since a temperature gradient is generated between the sample and the thermometer when the temperature is rapidly increased, and a measurement error is generated, it is desirable that the temperature at the time of measuring the melting point is increased at a rate of 1 ℃ per minute or less.
Since the sample is prepared as fine powder as described above, the sample before melting is opaque due to diffuse reflection on the surface. The temperature at which the appearance of the sample begins to be transparent is generally set as the lower limit of the melting point, and the temperature at which the sample completely melts is set as the upper limit. Various types of measuring devices exist, and the most classical device uses the following: the capillary tube containing the sample was attached to a double-tube thermometer, and heated by a warm bath. For the purpose of attaching the capillary tube to the double-tube type thermometer, a liquid having high viscosity is used as a liquid for a hot bath, and concentrated sulfuric acid or silicone oil is often used, and the sample is attached so as to move to the vicinity of a reservoir at the distal end of the thermometer. The following apparatus can be used as the melting point measuring apparatus: the melting point was automatically determined by heating with a metal heating block (heat block) while adjusting the heating while measuring the transmittance of light.
In the present specification, the melting point of 150 ℃ or lower means that the upper limit of the melting point is 150 ℃ or lower, and the melting point of 25 ℃ or higher means that the lower limit of the melting point is 25 ℃ or higher.
The content of the component (c) is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, based on the total amount of the binder composition (excluding the solvent).
(d) The components: high molecular component with weight average molecular weight of 10000 or more
The adhesive composition of the present embodiment may contain a polymer component ((d) component) having a weight average molecular weight of 10000 or more, as necessary. The adhesive composition containing the component (d) is further excellent in heat resistance and film-forming properties.
As the component (d), for example, a phenoxy resin, a polyimide resin, a polyamide resin, a polycarbodiimide resin, a cyanate resin, an acrylic resin, a polyester resin, a polyethylene resin, a polyether sulfone resin, a polyetherimide resin, a polyvinyl acetal resin, a urethane resin, and an acrylic rubber are preferable from the viewpoint of obtaining excellent heat resistance, film forming properties, and connection reliability. Among these, phenoxy resins, polyimide resins, acrylic rubbers, acrylic resins, cyanate ester resins, and polycarbodiimide resins are more preferable, phenoxy resins, polyimide resins, acrylic rubbers, and acrylic resins are more preferable, and phenoxy resins are particularly preferable, from the viewpoint of further excellent heat resistance and film-forming properties. These (d) components can also be used alone or as a mixture or copolymer of two or more. However, the component (d) does not contain an epoxy resin as the component (a).
(d) The weight average molecular weight of the component (A) is 10000 or more, preferably 20000 or more, and more preferably 30000 or more. The component (d) can further improve the heat resistance and film-forming property of the adhesive composition.
The weight average molecular weight of the component (d) is preferably 1000000 or less, more preferably 500000 or less. The component (d) has an effect of high heat resistance.
The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography). An example of measurement conditions of the GPC method is shown below.
The device comprises the following steps: HCL-8320GPC, UV-8320 (product name, manufactured by TOSOH CORPORATION), or HPLC-8020 (product name, manufactured by TOSOH CORPORATION)
Pipe column: TSK gel super Multipore HZ-Mx 2, or two pieces of GMHXL + one piece of G-2000XL (2pieces of GMHXL +1piece of G-2000XL)
A detector: RI or UV detector
Temperature of the pipe column: 25-40 deg.C
Eluent: the solvent for dissolving the polymer component is selected. For example, THF (tetrahydrofuran), DMF (N, N-dimethylformamide), DMA (N, N-dimethylacetamide), NMP (N-methylpyrrolidone), toluene. When a polar solvent is selected, the concentration of phosphoric acid is adjusted to 0.05 to 0.1mol/L (usually 0.06mol/L) and the concentration of LiBr is adjusted to 0.5 to 1.0mol/L (usually 0.63 mol/L).
Flow rate: 0.3 mL/min to 1.5 mL/min
Standard substance: polystyrene
When the adhesive composition contains the component (d), the content C of the component (a)aContent C relative to component (d)dRatio of Ca/CdThe mass ratio is preferably 0.01 to 5, more preferably 0.05 to 3, and still more preferably 0.1 to 2. If will be compared with Ca/CdWhen the amount is 0.01 or more, more favorable curability and adhesion can be obtained, and the ratio C is adjusted toa/CdWhen the film forming property is 5 or less, a more favorable film forming property can be obtained.
(e) The components: filler material
The adhesive composition of the present embodiment may contain a filler (component (e)) as required. The viscosity of the adhesive composition, the physical properties of the cured product of the adhesive composition, and the like can be controlled by the component (e). Specifically, according to the component (e), for example, generation of voids at the time of connection can be suppressed, and the moisture absorption rate of a cured product of the adhesive composition can be reduced.
As the component (e), an insulating inorganic filler, whisker, resin filler, or the like can be used. Further, as the component (e), one kind may be used alone, or two or more kinds may be used in combination.
Examples of the insulating inorganic filler include: glass, silica, alumina, titania, carbon black, mica, and boron nitride. Among these, silica, alumina, titania and boron nitride are preferable, and silica, alumina and boron nitride are more preferable.
Examples of whiskers include: aluminum borate, aluminum titanate, zinc oxide, calcium silicate, magnesium sulfate, and boron nitride.
Examples of the resin filler include fillers containing resins such as polyurethane and polyimide.
The resin filler has a smaller thermal expansion coefficient than organic components (epoxy resin, curing agent, and the like), and therefore has an excellent effect of improving connection reliability. Further, the viscosity of the adhesive composition can be easily adjusted depending on the resin filler. Further, the resin filler is superior in stress relaxation function to the inorganic filler, and therefore, peeling in a reflow test or the like can be further suppressed by the resin filler.
Since the inorganic filler has a smaller thermal expansion coefficient than the resin filler, the inorganic filler can reduce the thermal expansion coefficient of the adhesive composition. Further, since many inorganic fillers are general-purpose ones and the particle diameter is controlled, it is also preferable for adjusting the viscosity.
Since the resin filler and the inorganic filler each have an advantageous effect, either one may be used depending on the application, or both may be mixed and used in order to exhibit the functions of both.
(e) The shape, particle size and content of the component are not particularly limited. The component (e) may be surface-treated to appropriately adjust physical properties.
The content of the component (e) is preferably 10 to 80% by mass, more preferably 15 to 60% by mass, based on the total amount of the binder composition (excluding the solvent).
(e) The component is preferably made of an insulator. If the component (e) is made of a conductive material (e.g., solder, gold, silver, copper, etc.), insulation reliability (particularly HAST resistance) may be reduced.
(other Components)
The adhesive composition of the present embodiment may contain additives such as an antioxidant, a silane coupling agent, a titanium coupling agent, a leveling agent, and an ion scavenger. These can be used alone or in combination of two or more. The amount of these additives may be appropriately adjusted so that the effects of the respective additives are exhibited.
The film-shaped adhesive (adhesive layer) 2 can be formed by dissolving or dispersing an adhesive composition containing the above-mentioned components in a solvent to prepare a varnish, applying the varnish on the supporting substrate 1, and removing the solvent by heating.
As the supporting substrate 1, for example, a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate can be used. Examples of commercially available products include polyethylene terephthalate films such as "A-31" manufactured by Teijin Dupont Film Japan Limited. The thickness of the support substrate 1 is preferably 10 μm to 100. mu.m, more preferably 30 μm to 75 μm, and particularly preferably 35 μm to 50 μm. If the thickness is less than 10 μm, the support base material 1 tends to be easily broken during coating, and if it exceeds 100 μm, the cost performance tends to be poor.
Examples of the method for applying the varnish to the supporting substrate 1 include: a generally known method such as a blade coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, or the like.
The temperature condition for removing the solvent by heating is preferably about 70 to 150 ℃.
The solvent to be used is not particularly limited, and is preferably determined in consideration of volatility and the like at the time of forming the binder layer according to the boiling point. Specifically, in terms of the difficulty in curing the adhesive layer at the time of forming the adhesive layer, a solvent having a relatively low boiling point such as methanol, ethanol, 2-methylethyl ketone, 2-ethoxyethanol, 2-butoxyethanol, methylethyl ketone, acetone, methylisobutyl ketone, toluene, xylene, or the like is preferable. For the purpose of improving coatability, a solvent having a relatively high boiling point, such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and cyclohexanone, can be used. These solvents can be used alone or in combination of two or more.
The thickness of the film-like adhesive (adhesive layer) 2 may be 2 to 50 μm, preferably 5 to 20 μm, and more preferably 5 to 16 μm from the viewpoint of suppressing the overflow of the resin after mounting.
The thickness of the film-like adhesive (adhesive layer) 2 may be 0.6 to 1.5 times, 0.7 to 1.3 times, or 0.8 to 1.2 times the height of the electrode before the semiconductor wafer is connected. The thickness of the film-like adhesive (adhesive layer) 2 may also be smaller than the electrode height before the semiconductor wafer connection. When the thickness of the adhesive layer 2 is 0.6 times or more the height of the electrode, generation of voids due to non-filling of the adhesive can be sufficiently suppressed, and connection reliability can be further improved. Further, if the thickness is 1.5 times or less, the amount of the adhesive pushed out from the chip connection region at the time of connection can be sufficiently suppressed, so that the fillet can be suppressed from being generated, and the adhesive can be sufficiently prevented from adhering to an unnecessary portion.
The viscosity of the film-like adhesive (adhesive layer) 2 at 80 ℃ is preferably 4000 pas to 10000 pas, more preferably 5000 pas to 9000 pas. When the viscosity is within the above range, the resin is easily melted at the time of pressure bonding, and the resin can sufficiently flow, so that voids are less likely to be generated around the electrodes and the grooves, and further, as a preliminary stage for obtaining good connection, contact between the opposing electrodes can be more reliably achieved. The viscosity of the adhesive layer 2 was measured in the following order. First, a plurality of film-like adhesives are bonded at a temperature of 60 to 80 ℃ to prepare a measurement sample having a thickness of 400 to 600 μm. For the measurement sample, ARES (TA Instruments, manufactured by inc., product name) was used, and the diameter of the measurement jig was measured: 8mm, measurement frequency: 10Hz, measurement temperature range: 25 ℃ to 260 ℃, temperature rise rate: the viscosity was measured at 10 ℃/min to determine the viscosity at a predetermined temperature.
The viscosity of the film-shaped adhesive (adhesive layer) 2 can be adjusted by, for example, selecting a high molecular weight component, selecting a filler, and adjusting the amount of these components.
Next, the back grinding tape 5 will be explained.
The pressure-sensitive adhesive layer 3 has adhesive force at room temperature, and preferably has necessary adhesive force with respect to the adherend. Further, it preferably has a property of being cured (adhesive force is reduced) by high energy rays such as radiation or heat, but more preferably, it can be easily peeled from the adhesive layer without applying high energy rays such as radiation or heat. Also, the pressure-sensitive adhesive layer 3 may be a pressure-sensitive type pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer 3 can be formed using, for example, an acrylic resin, various synthetic rubbers, natural rubber, and a polyimide resin.
When the pressure-sensitive adhesive layer 3 has a property of being cured (adhesive force is reduced) by high energy rays such as radiation, the pressure-sensitive adhesive layer 3 may contain, for example, an acrylic copolymer as a main component, a crosslinking agent, and a photopolymerization initiator. These components are explained below. In the present specification, the term "main component" refers to a component contained in an amount of more than 50 parts by mass per 100 parts by mass of the composition constituting the object layer.
The acrylic copolymer has at least a group containing an actinic ray-curable carbon-carbon double bond and a hydroxyl group in the main chain.
An acrylic resin or a methacrylic resin (hereinafter referred to as a "(meth) acrylic resin") as an acrylic copolymer may contain an unsaturated bond in a side chain and the resin itself may have tackiness. Examples of such resins include those having a glass transition temperature of-40 ℃ or lower, a hydroxyl value of 20mgKOH/g to 150mgKOH/g, a chain-polymerizable functional group of 0.3mmol/g to 1.5mmol/g, a substantially undetectable acid value, and a weight average molecular weight of 30 ten thousand or more.
The (meth) acrylic resin having such characteristics can be synthesized by a known method, and for example, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, a precipitation polymerization method, a gas phase polymerization method, a plasma polymerization method, a supercritical polymerization method, or the like can be used. As the type of the polymerization reaction, not only radical polymerization, cationic polymerization, anionic polymerization, living radical polymerization, living cationic polymerization, living anionic polymerization, coordination polymerization, immortal polymerization (immortal polymerization), and the like, but also ATRP, RAFT, and the like can be used. Among these, the case of using a solution polymerization method and performing synthesis by radical polymerization is preferable because it is not only economical, high in reaction rate, easy to control polymerization, and the like, but also has ease of blending, and the like, by directly using a resin solution obtained by polymerization.
Here, a method of obtaining a (meth) acrylic resin by radical polymerization using a solution polymerization method will be described in detail as an example.
The monomer that can be used in synthesizing the (meth) acrylic resin is not particularly limited as long as it has one (meth) acrylic group in one molecule, and specific examples thereof include: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl heptyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and mixtures thereof, Aliphatic (meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, and mono (2- (meth) acryloyloxyethyl) succinate; alicyclic (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, and mono (2- (meth) acryloyloxyethyl) hexahydrophthalate; benzyl (meth) acrylate, phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, 1-naphthyloxyethyl (meth) acrylate, 2-naphthyloxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (orthophenylphenoxy) propyl (meth) acrylate, phenylbenzyl (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, o-phenylphenoxy ethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, aromatic (meth) acrylates such as 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate and 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate; heterocyclic (meth) acrylates such as 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethylhexahydrophthalimide, and 2- (meth) acryloyloxyethyl-N-carbazole; these caprolactone modifications; omega-carboxy-polycaprolactone mono (meth) acrylate; glycidyl (meth) acrylate, glycidyl a-ethyl (meth) acrylate, glycidyl a-propyl (meth) acrylate, glycidyl a-butyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-propylglycidyl (meth) acrylate, compounds having an ethylenically unsaturated group and an epoxy group such as 3, 4-epoxybutyl (meth) acrylate, 3, 4-epoxyheptyl (meth) acrylate, α -ethyl-6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like; compounds having an ethylenically unsaturated group and an oxetanyl group such as (2-ethyl-2-oxetanyl) methyl (meth) acrylate, (2-methyl-2-oxetanyl) methyl (meth) acrylate, 2- (2-ethyl-2-oxetanyl) ethyl (meth) acrylate, 2- (2-methyl-2-oxetanyl) ethyl (meth) acrylate, 3- (2-ethyl-2-oxetanyl) propyl (meth) acrylate, and 3- (2-methyl-2-oxetanyl) propyl (meth) acrylate; compounds having an ethylenically unsaturated group and an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate; compounds having an ethylenically unsaturated group and a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate can be appropriately combined to obtain the desired composition.
Further, if necessary, styrene, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-2-methyl-2-propylmaleimide, N-pentylmaleimide, N-2-pentylmaleimide, N-3-pentylmaleimide, N-2-methyl-1-butylmaleimide, N-2-methyl-2-butylmaleimide, N-3-methyl-1-butylmaleimide, N-3-methyl-2-butylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-2-methyl-2-propylmaleimide, N-pentylmaleimide, N-2-methyl-1-butylmaleimide, N-3-methyl-, N-hexylmaleimide, N-2-hexylmaleimide, N-3-hexylmaleimide, N-2-methyl-1-pentylmaleimide, N-2-methyl-2-pentylmaleimide, N-2-methyl-3-pentylmaleimide, N-3-methyl-1-pentylmaleimide, N-3-methyl-2-pentylmaleimide, N-3-methyl-3-pentylmaleimide, N-4-methyl-1-pentylmaleimide, N-4-methyl-2-pentylmaleimide, N-2, 2-dimethyl-1-butylmaleimide, N-2-methyl-1-pentylmaleimide, N-2-methyl-2-pentylmaleimide, N-2-methyl-1-, N-3, 3-dimethyl-1-butylmaleimide, N-3, 3-dimethyl-2-butylmaleimide, N-2, 3-dimethyl-1-butylmaleimide, N-2, 3-dimethyl-2-butylmaleimide, N-hydroxymethylmaleimide, N-1-hydroxyethylmaleimide, N-2-hydroxyethylmaleimide, N-1-hydroxy-1-propylmaleimide, N-2-hydroxy-1-propylmaleimide, N-3-hydroxy-1-propylmaleimide, N-1-hydroxy-2-propylmaleimide, N-2-butylmaleimide, N-2-butyl, N-2-hydroxy-2-propylmaleimide, N-1-hydroxy-1-butylmaleimide, N-2-hydroxy-1-butylmaleimide, N-3-hydroxy-1-butylmaleimide, N-4-hydroxy-1-butylmaleimide, N-1-hydroxy-2-butylmaleimide, N-2-hydroxy-2-butylmaleimide, N-3-hydroxy-2-butylmaleimide, N-4-hydroxy-2-butylmaleimide, N-2-methyl-3-hydroxy-1-propylmaleimide, N-2-hydroxy-2-butylmaleimide, N-2-hydroxy-1-butylmaleimide, N-2, N-2-methyl-3-hydroxy-2-propylmaleimide, N-2-methyl-2-hydroxy-1-propylmaleimide, N-1-hydroxy-1-pentylmaleimide, N-2-hydroxy-1-pentylmaleimide, N-3-hydroxy-1-pentylmaleimide, N-4-hydroxy-1-pentylmaleimide, N-5-hydroxy-1-pentylmaleimide, N-1-hydroxy-2-pentylmaleimide, N-2-hydroxy-2-pentylmaleimide, N-3-hydroxy-2-pentylmaleimide, N-2-hydroxy-1-pentylmaleimide, N-2-pentylmaleimide, N, N-4-hydroxy-2-pentylmaleimide, N-5-hydroxy-2-pentylmaleimide, N-1-hydroxy-3-pentylmaleimide, N-2-hydroxy-3-pentylmaleimide, N-3-hydroxy-3-pentylmaleimide, N-1-hydroxy-2-methyl-1-butylmaleimide, N-1-hydroxy-2-methyl-2-butylmaleimide, N-1-hydroxy-2-methyl-3-butylmaleimide, N-1-hydroxy-2-methyl-4-butylmaleimide, N-2-pentylmaleimide, N-1-hydroxy-3-pentylmaleimide, N-2-methyl-1-butylmaleimide, N-2-methyl-3-butylmaleimide, N-2, N-2-hydroxy-2-methyl-1-butylmaleimide, N-2-hydroxy-2-methyl-3-butylmaleimide, N-2-hydroxy-2-methyl-4-butylmaleimide, N-2-hydroxy-3-methyl-1-butylmaleimide, N-2-hydroxy-3-methyl-2-butylmaleimide, N-2-hydroxy-3-methyl-3-butylmaleimide, N-2-hydroxy-3-methyl-4-butylmaleimide, N-4-hydroxy-2-methyl-1-butylmaleimide, N-2-hydroxy-3-methyl-4-butylmaleimide, N-2-hydroxy-3-methyl-1-butylmaleimide, N-2-hydroxy-methyl-3-butylmaleimide, N-2-hydroxy-methyl-1-butylmaleimide, N-2, N-4-hydroxy-2-methyl-2-butylmaleimide, N-1-hydroxy-3-methyl-1-butylmaleimide, N-1-hydroxy-2, 2-dimethyl-1-propylmaleimide, N-3-hydroxy-2, 2-dimethyl-1-propylmaleimide, N-1-hydroxy-1-hexylmaleimide, N-1-hydroxy-2-hexylmaleimide, N-1-hydroxy-3-hexylmaleimide, N-1-hydroxy-4-hexylmaleimide, N-2-butylmaleimide, N-1-hydroxy-3-butylmaleimide, N-1-hydroxy-2-butylmaleimide, N-1-hydroxy-3, N-1-hydroxy-5-hexylmaleimide, N-1-hydroxy-6-hexylmaleimide, N-2-hydroxy-1-hexylmaleimide, N-2-hydroxy-2-hexylmaleimide, N-2-hydroxy-3-hexylmaleimide, N-2-hydroxy-4-hexylmaleimide, N-2-hydroxy-5-hexylmaleimide, N-2-hydroxy-6-hexylmaleimide, N-3-hydroxy-1-hexylmaleimide, N-3-hydroxy-2-hexylmaleimide, N-3-hydroxy-3-hexylmaleimide, N-5-hydroxy-5-hexylmaleimide, N-2-hydroxy-6-hexylmaleimide, N-3-hydroxy-1-hexylmaleimide, N-2-hexylmaleimide, N-3-hydroxy-3-hexylmaleimide, N-2-, N-3-hydroxy-4-hexylmaleimide, N-3-hydroxy-5-hexylmaleimide, N-3-hydroxy-6-hexylmaleimide, N-1-hydroxy-2-methyl-1-pentylmaleimide, N-1-hydroxy-2-methyl-2-pentylmaleimide, N-1-hydroxy-2-methyl-3-pentylmaleimide, N-1-hydroxy-2-methyl-4-pentylmaleimide, N-1-hydroxy-2-methyl-5-pentylmaleimide, N-2-hydroxy-2-methyl-1-pentylmaleimide, n-2-hydroxy-2-methyl-2-pentylmaleimide, N-2-hydroxy-2-methyl-3-pentylmaleimide, N-2-hydroxy-2-methyl-4-pentylmaleimide, N-2-hydroxy-2-methyl-5-pentylmaleimide, N-2-hydroxy-3-methyl-1-pentylmaleimide, N-2-hydroxy-3-methyl-2-pentylmaleimide, N-2-hydroxy-3-methyl-3-pentylmaleimide, N-2-hydroxy-3-methyl-4-pentylmaleimide, N-2-hydroxy-2-pentylmaleimide, N-2-methyl-4, N-2-hydroxy-3-methyl-5-pentylmaleimide, N-2-hydroxy-4-methyl-1-pentylmaleimide, N-2-hydroxy-4-methyl-2-pentylmaleimide, N-2-hydroxy-4-methyl-3-pentylmaleimide, N-2-hydroxy-4-methyl-4-pentylmaleimide, N-2-hydroxy-4-methyl-5-pentylmaleimide, N-3-hydroxy-2-methyl-1-pentylmaleimide, N-3-hydroxy-2-methyl-2-pentylmaleimide, N-2-hydroxy-4-pentylmaleimide, N-2-methyl-1, N-3-hydroxy-2-methyl-3-pentylmaleimide, N-3-hydroxy-2-methyl-4-pentylmaleimide, N-3-hydroxy-2-methyl-5-pentylmaleimide, N-1-hydroxy-4-methyl-1-pentylmaleimide, N-1-hydroxy-4-methyl-2-pentylmaleimide, N-1-hydroxy-4-methyl-3-pentylmaleimide, N-1-hydroxy-4-methyl-4-pentylmaleimide, N-1-hydroxy-3-methyl-1-pentylmaleimide, N-2-hydroxy-4-methyl-3-pentylmaleimide, N-1-hydroxy-4-methyl-1-pentylmaleimide, N-2-methyl, N-1-hydroxy-3-methyl-2-pentylmaleimide, N-1-hydroxy-3-methyl-3-pentylmaleimide, N-1-hydroxy-3-methyl-4-pentylmaleimide, N-1-hydroxy-3-methyl-5-pentylmaleimide, N-3-hydroxy-3-methyl-1-pentylmaleimide, N-3-hydroxy-3-methyl-2-pentylmaleimide, N-1-hydroxy-3-ethyl-4-butylmaleimide, N-2-hydroxy-3-ethyl-4-butylmaleimide, N-1-hydroxy-3-methyl-4-pentylmaleimide, N-2-hydroxy-3-ethyl-4-butylmaleimide, N-2-hydroxy-3-methyl-4-pentylmaleimide, N-2-hydroxy-2-ethyl-1-butylmaleimide, N-4-hydroxy-3-ethyl-2-butylmaleimide, N-4-hydroxy-3-ethyl-3-butylmaleimide, N-4-hydroxy-3-ethyl-4-butylmaleimide, N-1-hydroxy-2, 3-dimethyl-1-butylmaleimide, N-1-hydroxy-2, 3-dimethyl-2-butylmaleimide, N-1-hydroxy-2, 3-dimethyl-3-butylmaleimide, N-1-hydroxy-2, 3-dimethyl-4-butylmaleimide, N-2-hydroxy-2, 3-dimethyl-1-butylmaleimide, N-2-hydroxy-2, 3-dimethyl-3-butylmaleimide, N-2-hydroxy-2, 3-dimethyl-4-butylmaleimide, N-1-hydroxy-2, 2-dimethyl-1-butylmaleimide, N-1-hydroxy-2, 2-dimethyl-3-butylmaleimide, N-1-hydroxy-2, alkyl maleimides such as 2-dimethyl-4-butylmaleimide, N-2-hydroxy-3, 3-dimethyl-1-butylmaleimide, N-2-hydroxy-3, 3-dimethyl-2-butylmaleimide, N-2-hydroxy-3, 3-dimethyl-4-butylmaleimide, N-1-hydroxy-3, 3-dimethyl-1-butylmaleimide, N-1-hydroxy-3, 3-dimethyl-2-butylmaleimide, and N-1-hydroxy-3, 3-dimethyl-4-butylmaleimide; cycloalkyl maleimides such as N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-2-methylcyclohexylmaleimide, N-2-ethylcyclohexylmaleimide and N-2-chlorocyclohexylmaleimide; and arylmaleimides such as N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, and N-2-chlorophenylmaleimide.
Among them, at least one selected from the group consisting of (meth) acrylic esters which are aliphatic esters having C8 to C23 is preferably used. The (meth) acrylic resin obtained by copolymerizing such monomer components is preferably one having a low glass transition temperature, and therefore exhibits excellent adhesive properties and a strong hydrophobic interaction, and therefore has excellent releasability at the interface between the pressure-sensitive adhesive layer 3 and the adhesive layer 2 after irradiation with ultraviolet rays or an electron beam.
The polymerization initiator necessary for obtaining such a (meth) acrylic resin is not particularly limited as long as it is a compound that generates radicals by heating at 30 ℃ or higher, and examples thereof include: ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; peroxyketals such as 1, 1-bis (t-butylperoxy) cyclohexane, 1-bis (t-butylperoxy) -2-methylcyclohexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, and the like; hydrogen peroxide such as p-menthane hydrogen peroxide; dialkyl peroxides such as α, α' -bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide; diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide and benzoyl peroxide; peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and di-3-methoxybutyl peroxycarbonate; tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,3, 3-tetramethylbutylperoxy-2-ethylhexanoic acid, 2, 5-dimethyl-2, 5-bis (2-ethylhexanoylperoxy) hexane, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-hexylperoxyisopropyl monocarbonate, tert-butyl 3,5, 5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, peroxyesters such as t-butyl peroxybenzoate, t-hexyl peroxybenzoate, 2, 5-dimethyl-2, 5-bis (benzoyl peroxide) hexane, and t-butyl peroxyacetate; 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2' -dimethylvaleronitrile), and the like.
The reaction solvent used in the solution polymerization is not particularly limited as long as the (meth) acrylic resin can be dissolved therein, and examples thereof include: aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, and p-cymene; cyclic ethers such as tetrahydrofuran and 1, 4-dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ -butyrolactone, and the like; carbonates such as ethylene carbonate and propylene carbonate; polyhydric alcohol alkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; polyhydric alcohol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; amides such as N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and these organic solvents can be used alone or in combination of two or more kinds. Further, the polymerization can be carried out using supercritical carbon dioxide or the like as a solvent.
The (meth) acrylic resin can be provided with photosensitivity by chemically bonding a functional group that can react by irradiation with ultraviolet light, electron beams, or visible light to the (meth) acrylic resin. The functional group which can be reacted by irradiation with ultraviolet light, electron beam, or visible light as used herein means, for example, (meth) acrylic group, vinyl group, allyl group, glycidyl group, alicyclic epoxy group, oxetanyl group, and the like.
The method for imparting photosensitivity to the (meth) acrylic resin is not particularly limited, and, for example, photosensitivity can be imparted to the (meth) acrylic resin by: when the above-mentioned (meth) acrylic resin is synthesized, a monomer having a functional group capable of undergoing an addition reaction in advance, for example, a hydroxyl group, a carboxyl group, a maleic anhydride group, a glycidyl group, an amino group, or the like is copolymerized to introduce the functional group capable of undergoing an addition reaction into the (meth) acrylic resin, and in addition, at least one ethylenically unsaturated group is subjected to an addition reaction with a compound having at least one functional group selected from an epoxy group, an oxetanyl group, an isocyanate group, a hydroxyl group, a carboxyl group, or the like, thereby introducing the ethylenically unsaturated group into the side chain.
Such a compound is not particularly limited, and there may be mentioned: glycidyl (meth) acrylate, glycidyl a-ethyl (meth) acrylate, glycidyl a-propyl (meth) acrylate, glycidyl a-butyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-propylglycidyl (meth) acrylate, compounds having an ethylenically unsaturated group and an epoxy group such as 3, 4-epoxybutyl (meth) acrylate, 3, 4-epoxyheptyl (meth) acrylate, α -ethyl-6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like; compounds having an ethylenically unsaturated group and an oxetanyl group such as (2-ethyl-2-oxetanyl) methyl (meth) acrylate, (2-methyl-2-oxetanyl) methyl (meth) acrylate, 2- (2-ethyl-2-oxetanyl) ethyl (meth) acrylate, 2- (2-methyl-2-oxetanyl) ethyl (meth) acrylate, 3- (2-ethyl-2-oxetanyl) propyl (meth) acrylate, and 3- (2-methyl-2-oxetanyl) propyl (meth) acrylate; compounds having an ethylenically unsaturated group and an isocyanate group such as methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2-acryloxyethyl isocyanate, and m-isopropenyl- α, α -dimethylbenzyl isocyanate; compounds having an ethylenically unsaturated group and a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate; and compounds having an ethylenically unsaturated group and a carboxyl group such as (meth) acrylic acid, crotonic acid, cinnamic acid, succinic acid (2- (meth) acryloyloxyethyl ester), 2-phthaloyl ethyl (meth) acrylate, 2-tetrahydrophthaloyl ethyl (meth) acrylate, 2-hexahydrophthaloyl ethyl (meth) acrylate, ω -carboxy-polycaprolactone mono (meth) acrylate, 3-vinylbenzoic acid, and 4-vinylbenzoic acid.
Among these, from the viewpoint of cost and reactivity, it is preferable to use 2- (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, ethyl isothiocyanate (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid, crotonic acid, 2-hexahydrophthaloyl ethyl (meth) acrylate, and the like to react with a (meth) acrylic resin to impart photosensitivity. These compounds can be used alone or in combination of two or more types. If necessary, a catalyst for accelerating the addition reaction or a polymerization inhibitor may be added for the purpose of avoiding the cleavage of the double bond during the reaction. Further, a reactant of an OH group-containing (meth) acrylic resin and at least one selected from 2-methacryloyloxyethyl isocyanate and 2-acryloxyethyl isocyanate is more preferable.
The crosslinking agent is a compound having two or more functional groups in one molecule, which are selected from at least one of hydroxyl group, glycidyl group, amino group, and the like introduced into the (meth) acrylic resin, and which are reactive with these functional groups, and the structure thereof is not limited. The bond formed by such a crosslinking agent includes an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a urea bond, and the like. Among these, the case where the crosslinking agent has an aromatic group-containing isocyanate group is preferable because the peeling force between the pressure-sensitive adhesive layer 3 and the adhesive layer 2 is not easily increased even if the ultraviolet irradiation amount is increased.
The amount of the crosslinking agent contained in the pressure-sensitive adhesive layer 3 is preferably 10 to 13 parts by mass with respect to 100 parts by mass of the acrylic copolymer. If the amount of the crosslinking agent is less than 10 parts by mass, the elongation at break of the pressure-sensitive adhesive layer 3 before ultraviolet irradiation becomes high, and the machinability in the dicing step tends to become insufficient. In addition, the peeling force between the pressure-sensitive adhesive layer 3 and the adhesive layer 2 after the ultraviolet irradiation is not sufficiently reduced, and it is likely to occur that the push-up amount at the time of the pickup process needs to be set relatively large. On the other hand, if the amount of the crosslinking agent exceeds 13 parts by mass, the adhesive force with the pressure-sensitive adhesive layer 3 before ultraviolet irradiation tends to be insufficient.
The crosslinking agent preferably has two or more isocyanate groups in one molecule. When such a compound is used, it can easily react with a hydroxyl group, a glycidyl group, an amino group, or the like introduced into the (meth) acrylic resin to form a strong crosslinked structure, thereby suppressing adhesion of the pressure-sensitive adhesive layer 3 to the semiconductor chip after the die bonding step.
Here, the crosslinking agent having two or more isocyanate groups in one molecule means, specifically exemplified, that: isocyanate compounds such as 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, diphenylmethane-4, 4 '-diisocyanate, diphenylmethane-2, 4' -diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, dicyclohexylmethane-2, 4' -diisocyanate, and lysine isocyanate.
Further, an isocyanate group-containing oligomer obtained by reacting the isocyanate compound with a polyol having two or more OH groups in one molecule can also be used. In the case of obtaining such an oligomer, examples of the polyol having two or more OH groups in one molecule include: ethylene glycol, propylene glycol, butylene glycol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 11-undecanediol, 1, 12-dodecanediol, glycerol, pentaerythritol, dipentaerythritol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, and the like.
Among these, the crosslinking agent is more preferably a reactant of a polyfunctional isocyanate having two or more isocyanate groups in one molecule and a polyol having three or more OH groups in one molecule. By using such isocyanate group-containing oligomer, the pressure-sensitive adhesive layer 3 can form a dense crosslinked structure.
The photopolymerization initiator is not particularly limited as long as it generates an active species capable of chain-polymerizing the acrylic copolymer by irradiating one or more light selected from ultraviolet rays, electron beams, and visible light, and may be, for example, a photo radical polymerization initiator or a photo cation polymerization initiator. The chain polymerizable active species is not particularly limited as long as it is an active species that initiates the polymerization reaction by reacting with the functional group of the acrylic copolymer.
Examples of the photo radical polymerization initiator include: benzoketals such as 2, 2-dimethoxy-1, 2-diphenylethan-1-one; α -hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, and 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one; α -aminoketones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one; oxime esters such as 1- [4- (phenylthio) phenyl ] -1, 2-octanedione-2- (benzoyl) oxime; phosphine oxides such as bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide, and 2,4, 6-trimethylbenzoyl diphenylphosphine oxide; 2,4, 5-triarylimidazole dimers such as 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer; benzophenone compounds such as benzophenone, N ' -tetramethyl-4, 4' -diaminobenzophenone, N ' -tetraethyl-4, 4' -diaminobenzophenone, and 4-methoxy-4 ' -dimethylaminobenzophenone; quinone compounds such as 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, and 2, 3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin and the like; benzyl compounds such as benzyl dimethyl ketal; acridine compounds such as 9-phenylacridine, 1, 7-bis (9,9' -acridinylheptane): n-phenylglycine, coumarin, and the like.
In the 2,4, 5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole positions may be the same to provide a symmetrical compound, or may be different to provide an asymmetrical compound. Further, the thioxanthone compound may be combined with a tertiary amine as in the combination of diethylthioxanthone and dimethylaminobenzoic acid.
Examples of the photo cation polymerization initiator include: aryl diazonium salts such as p-methoxybenzene diazonium hexafluorophosphate and the like, diaryl iodonium salts such as diphenyl iodonium hexafluorophosphate and diphenyl iodonium hexafluoroantimonate and the like; triaryl sulfonium salts such as triphenyl sulfonium hexafluorophosphate, triphenyl sulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy phenyl sulfonium hexafluorophosphate, diphenyl-4-thiophenoxy phenyl sulfonium hexafluoroantimonate, diphenyl-4-thiophenoxy phenyl sulfonium pentafluoro hydroxy antimonate, and the like; triaryl selenium salts such as triphenyl selenium hexafluorophosphate, triphenyl selenium tetrafluoroborate, triphenyl selenium hexafluoroantimonate, and the like; dialkylphenacylsulfonium salts such as dimethylbenzoylmethylsulfonium hexafluoroantimonate and diethylphenacylsulfonium hexafluoroantimonate; dialkyl-4-hydroxy salts such as 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate and 4-hydroxyphenyl benzylmethylthioninium hexafluoroantimonate; sulfonic acid esters such as α -hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate, α -sulfonyloxy ketone, and β -sulfonyloxy ketone, and these cationic polymerization initiators can be used alone or in combination of two or more kinds. Furthermore, it can be used in combination with an appropriate sensitizer.
Among them, in the case where the pressure-sensitive adhesive layer 3 requires strict insulation and insulation reliability, a photo radical initiator, in particular, a benzoketal such as 2, 2-dimethoxy-1, 2-diphenylethane-1-one is preferably used; alpha-hydroxyketones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, benzophenone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1, 2-phenylanthraquinone, quinone compounds such as 2, 3-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, and 2, 3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin and the like; benzyl compounds such as benzyl dimethyl ketal; acridine compounds such as 9-phenylacridine, 1, 7-bis (9,9' -acridinylheptane): n-phenylglycine, coumarin and the like are preferable because of excellent storage stability, and 2, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, benzophenone are more preferable because they can be treated under a general ultraviolet-shielding fluorescent lamp without facilities such as a yellow room (yellow room).
The amount of the photopolymerization initiator to be added varies depending on the thickness of the pressure-sensitive adhesive layer 3 to be targeted and the light source to be used, and is preferably 0.5 to 1.5 parts by mass based on 100 parts by mass of the acrylic copolymer. If the amount of the photopolymerization initiator is 0.5 parts by mass or more, the peeling force from the adhesive layer 2 after the ultraviolet irradiation can be sufficiently reduced. If the amount of the photopolymerization initiator is 1.5 parts by mass or less, the decomposition of the pressure-sensitive adhesive layer 3 can be suppressed when irradiated with ultraviolet rays.
The thickness of the pressure-sensitive adhesive layer 3 is more than 3 times of the thickness of the adhesive layer 2. However, if the thickness of the pressure-sensitive adhesive layer 3 is excessively increased, the thickness variation becomes large and the cost of raw materials becomes large, so the thickness of the pressure-sensitive adhesive layer 3 is more preferably 3 to 5 times the thickness of the adhesive layer 2.
The thickness of the pressure-sensitive adhesive layer 3 is preferably 25 μm to 295 μm, more preferably 50 μm to 150 μm, and further preferably 50 μm to 100 μm. When the thickness is 25 μm or more, generation of voids at the time of laminating the adhesive layer 2 is more easily suppressed, and particularly, even when the difference between the height of the electrode and the thickness of the adhesive layer 2 is large, the occurrence of voids tends to be easily suppressed. On the other hand, when the thickness is 295 μm or less, the amount of the residual solvent in the pressure-sensitive adhesive layer 3 can be suppressed from increasing, and the variation in the adhesive force due to the influence of the residual solvent tends to be suppressed.
The pressure-sensitive adhesive layer 3 can be formed by dissolving or dispersing an adhesive composition containing the above-mentioned components in a solvent to prepare a varnish, applying the varnish on the substrate 4, and removing the solvent by heating.
Examples of the substrate 4 include: plastic films such as polyester films, polytetrafluoroethylene films, polyethylene films, polypropylene films, and polymethylpentene films. Among these, polyester films are preferable, and polyethylene terephthalate films are more preferable. The substrate 4 may be a substrate in which two or more kinds selected from the above materials are mixed, or a substrate in which the above film is multilayered.
Examples of the method for applying the varnish to the substrate 4 include: a generally known method such as a blade coating method, a roll coating method, a spray coating method, a gravure coating method, a bar coating method, a curtain coating method, a comma coating method, a die coating method, or the like.
The temperature condition for removing the solvent by heating is preferably about 70 to 150 ℃.
The solvent used may be the same solvent as that used for forming the adhesive layer 2.
The thickness of the substrate 4 is preferably 5 μm to 50 μm, and more preferably 12 μm to 38 μm. When the thickness is 5 μm or more, deformation of the base material 4 due to thermal shrinkage during the drying process of the pressure-sensitive adhesive layer 3 tends to be easily suppressed, and variation in the thickness of the pressure-sensitive adhesive layer 3 tends to be easily suppressed, and when the thickness is 50 μm or less, warpage of the wafer after back grinding tends to be more easily suppressed.
The back grinding tape 5 has a thickness of 75 to 300. mu.m, preferably 75 to 175 μm, and more preferably 85 to 125 μm. When the thickness is 75 μm or more, the occurrence of insufficient embedding of the bump peripheral portion and the scribe line tends to be suppressed, and when the thickness is 300 μm or less, the occurrence of bleeding of the pressure-sensitive adhesive layer 3 tends to be suppressed, and the adhesive layer 2 also tends to be easily peeled from the wafer when the back-grinding tape is peeled.
From the viewpoint of improving the conformability of the adhesive film for processing a semiconductor wafer to the irregularities on the semiconductor wafer and further suppressing the occurrence of voids, the elastic modulus of the back grinding tape 5 at 35 ℃ is preferably 1.5GPa or less.
Next, each step of the method for manufacturing a semiconductor device according to the present embodiment will be described.
Fig. 2 is a schematic cross-sectional view for explaining a method of manufacturing a semiconductor device according to the present embodiment. In the present embodiment, the adhesive film 10 for processing a semiconductor wafer is used to manufacture a semiconductor device. Fig. 2(a) is a schematic cross-sectional view showing one embodiment of a semiconductor wafer, and fig. 2(b) is a schematic cross-sectional view for explaining one step in the method for manufacturing a semiconductor device according to the present embodiment.
The semiconductor wafer used in the present embodiment includes a bump electrode (solder bump) 26 on one main surface of the semiconductor wafer 20. The protruding electrode 26 includes a bump 22 and a solder ball 24 disposed on the bump 22.
Examples of the semiconductor wafer 20 include a 6-inch wafer, an 8-inch wafer, and a 12-inch wafer, the surfaces of which have been subjected to an oxide film treatment. The bump 22 is not particularly limited, and may be a bump made of copper, silver, gold, or the like. The solder ball 24 may be a solder ball made of a conventionally known solder material such as a lead-containing solder or a lead-free solder.
On the main surface of the semiconductor wafer 20 on which the protruding electrode 26 is provided, a groove 28 is formed as a scribe line which is a mark at the time of dicing. The grooves 28 are formed by recesses having a depth of about 5 to 15 μm.
The thickness of the semiconductor wafer 20 before thinning can be set to a range of 250 μm to 800 μm. Typically, the diced semiconductor wafers have a thickness of 625 μm to 775 μm at a size of 6 inches to 12 inches.
The height of the bump 22 is preferably 5 μm to 50 μm from the viewpoint of semiconductor miniaturization. From the viewpoint of semiconductor miniaturization, the height of the solder ball 24 is preferably 2 μm to 30 μm.
In the method for manufacturing a semiconductor device according to the present embodiment, the supporting base 1 is peeled off from the adhesive film 10 for processing a semiconductor wafer, the film-like adhesive (adhesive layer) 2, the pressure-sensitive adhesive layer 3, and the base 4 are sequentially disposed on the surface of the semiconductor wafer 20 on which the solder bumps are formed (hereinafter referred to as "functional surface"), and pressure is applied to the semiconductor wafer 20 and the base 4 so that the tips of the solder balls 24 penetrate the adhesive layer 2 (see fig. 2 (b)). Further, although it is preferable that the tip of the solder ball penetrates the adhesive layer, even if the adhesive layer of about several micrometers remains at the tip of the solder ball, there is no problem as long as it does not affect the connectivity when the printed circuit board and the semiconductor chip are electrically connected via the solder ball. In the present embodiment, the bumps are easily exposed by vacuum laminating and bonding the adhesive layer 2 on the functional surface of the semiconductor wafer 20.
A method using a film (diaphragm), a method using a roller, a press method, and the like are laminated under vacuum, but the film method is preferable from the viewpoint of embeddability.
As the conditions for lamination, the lamination temperature is preferably: 50-100 ℃ and linear pressure: 0.5kgf/cm to 3.0kgf/cm, conveyance speed: 0.2 m/min to 2.0 m/min.
As conditions for using the vacuum laminated film system, the platen temperature is preferably: 20 ℃ to 60 ℃, membrane temperature: 50-100 ℃ and degassing time: 10sec to 100sec, pressing time: 10sec to 100sec, pressurization: 0.1MPa to 1.0 MPa. In the case of the film system, the lamination temperature refers to the film temperature.
When the lamination is performed at a high temperature exceeding 80 ℃, the wafer after the back grinding tends to be largely warped. On the other hand, if the lamination temperature is too low, it tends to be difficult to embed the bump periphery. Therefore, the lamination is preferably performed at 50 ℃ to 80 ℃.
Next, as shown in fig. 3, a step (back grinding step) of grinding the surface of the semiconductor wafer 20 opposite to the side on which the solder bumps (protruding electrodes) are formed to reduce the thickness of the semiconductor wafer 20 is performed.
Grinding can be performed with a back grinder. In this step, the semiconductor wafer 20 is preferably thinned to a thickness of 10 μm to 150 μm. If the thickness of the thinned semiconductor wafer 20 is less than 10 μm, the semiconductor wafer is likely to be damaged, while if it exceeds 150 μm, it is difficult to meet the demand for miniaturization of the semiconductor device.
Then, as shown in fig. 4(a), the polished surface side of the thinned semiconductor wafer 20 is attached to a dicing tape 6, and the semiconductor wafer 20 and the adhesive layer 2 are cut along the grooves 28 by using a dicing apparatus, thereby obtaining an adhesive-attached semiconductor chip composed of singulated semiconductor chips 20a and cut adhesive layers 2a (fig. 4 (b)). The back grinding tape 5 composed of the base material 4 and the pressure-sensitive adhesive layer 3 is peeled from the adhesive layer 2 before dicing.
By producing the semiconductor chip with the adhesive layer obtained as described above using the adhesive film 10 for semiconductor wafer processing according to the present invention, the vicinity of the bump electrode 26 and the vicinity of the portion having the groove 28 can be sufficiently embedded with the adhesive, no voids remain, and the tip of the solder ball can be sufficiently exposed from the adhesive.
After the dicing step is completed, the semiconductor chip with the adhesive is picked up by a pickup device and thermocompression bonded to the wiring circuit board.
In this embodiment, the semiconductor chip with the adhesive layer and another semiconductor chip having an electrode or the semiconductor chip mounting support member having an electrode are thermocompression bonded in two stages, i.e., a first thermocompression bonding step of applying pressure at a temperature lower than the melting point of the solder included in the solder bump in the direction in which the solder bump and the electrode face each other and a second thermocompression bonding step of bonding the solder bump and the electrode by melting the solder included in the solder bump by heating.
In the case where the adhesive layer further contains a flux component, the pressing in the first thermocompression bonding step may be performed at a temperature higher than the melting point or softening point of the flux component and lower than the melting point of the solder included in the solder bump. In this case, a more firm connection state can be obtained.
The conditions for the thermocompression bonding in the first thermocompression bonding step are preferably 100 to 200 ℃, pressure: 0.1MPa to 1.5MPa, time: 1 second to 15 seconds, more preferably temperature: 100 ℃ to 180 ℃, pressure: 0.1MPa to 1.0MPa, time: 1 second to 10 seconds. Further, as conditions for the thermocompression bonding in the second thermocompression bonding step, the temperature: 230 ℃ to 350 ℃, pressure: 0.1MPa to 1.5MPa, time: 1 second to 15 seconds, more preferably temperature: 230 ℃ to 300 ℃, pressure: 0.1MPa to 1.0MPa, time: 1 second to 15 seconds.
The conditions of temperature and pressure refer to the temperature and pressure applied to the adhesive layer.
Thus, the semiconductor device 100 shown in fig. 5 having the following structure is obtained: the electrodes 36 of the printed circuit board 7 and the bumps 22 of the semiconductor chip 20a are electrically connected via the solder balls 24, and the printed circuit board 7 and the semiconductor chip 20a are sealed with an adhesive 2 b.
In the method of manufacturing a semiconductor device according to the present embodiment, in order to sufficiently expose the tip of the solder ball from the adhesive layer and perform more reliable connection, it is preferable that the thickness of the adhesive layer 2 is smaller than the height of the solder bump 26, in the present embodiment, the total height T of the bump 22 and the solder ball 24, and the total thickness of the adhesive layer 2 and the substrate 4 is larger than the total height.
The method for manufacturing a semiconductor device according to the present embodiment may include the following steps in this order: a step (temporary bonding step) of temporarily bonding a substrate, another semiconductor chip, or a semiconductor wafer to a semiconductor chip by sandwiching a laminate between a pair of pressing members for temporary bonding that are opposed to each other, the laminate having the semiconductor chip, the substrate, the other semiconductor chip, or the semiconductor wafer including a portion corresponding to the other semiconductor chip, and a film-like adhesive disposed therebetween, and electrodes (connecting portions) of the semiconductor chip being disposed so as to be opposed to electrodes (connecting portions) of the substrate or the other semiconductor chip; and a step (main pressure bonding step) of electrically connecting the electrode (connection portion) of the semiconductor chip and the electrode (connection portion) of the substrate or another semiconductor chip by metal bonding.
In the above manufacturing method, when the stacked body is heated and pressed, at least one of the pair of pressing members for temporary pressure bonding used in the temporary pressure bonding step is heated to a temperature lower than a melting point of a metal material forming a surface of the connection portion of the semiconductor chip and a melting point of a metal material forming a surface of the connection portion of the substrate or another semiconductor chip.
In the main pressure bonding step, the laminate is heated to a temperature equal to or higher than at least one of the melting point of the metal material forming the surface of the connection portion of the semiconductor chip and the melting point of the metal material forming the surface of the connection portion of the substrate or another semiconductor chip. Here, the main pressure bonding step can be performed by, for example, the following method.
(first method)
The stacked body is sandwiched between a pair of main pressure-bonding pressing members, which are provided separately from the temporary pressure-bonding pressing member and face each other, and heated and pressed, whereby the connection portion of the semiconductor chip is electrically connected to the substrate or the connection portion of another semiconductor chip by metal bonding. In this case, when the stacked body is heated and pressed, at least one of the pair of pressing members for main pressure bonding is heated to a temperature equal to or higher than at least one of a melting point of a metal material forming a surface of the connection portion of the semiconductor chip or a melting point of a metal material forming a surface of the connection portion of the substrate or another semiconductor chip.
According to the above method, the step of temporarily pressure-bonding at a temperature lower than the melting point of the metal material on the surface on which the connection portion is formed and the step of permanently pressure-bonding at a temperature equal to or higher than the melting point of the metal material on the surface on which the connection portion is formed are performed using different pressure-bonding pressing members, whereby the time required for heating and cooling each pressure-bonding pressing member can be shortened. Therefore, the semiconductor device can be manufactured in a shorter time and with good productivity than when pressure bonding is performed using one pressure bonding pressing member. As a result, a large number of highly reliable semiconductor devices can be manufactured in a short time. The connection can be performed uniformly in the main pressure bonding step. In the case of performing the collective connection, since the semiconductor chips are pressure-bonded more in the main pressure bonding than in the temporary pressure bonding, the pressing member for pressure bonding having the pressure bonding head with a large area can be used. As described above, if the connection can be secured by collectively performing full-scale pressure bonding on a plurality of semiconductor chips, the productivity of the semiconductor device is improved.
(second method)
The connection portion of the semiconductor chip and the connection portion of the substrate or another semiconductor chip are electrically connected by metal bonding by holding the plurality of laminated bodies arranged on the stage or the laminated body having the plurality of semiconductor chips, the semiconductor wafer, and the adhesive and the unified connection sheet arranged so as to cover them by the stage and the pressure contact head facing the stage, and heating and pressing the plurality of laminated bodies in a unified manner. In this case, at least one of the stage and the pressure bonding head is heated to a temperature equal to or higher than at least one of a melting point of a metal material forming a surface of the connection portion of the semiconductor chip or a melting point of a metal material forming a surface of the connection portion of the substrate or another semiconductor chip.
According to the above method, when the plurality of semiconductor chips are collectively and formally pressure-bonded to the plurality of substrates, the plurality of other semiconductor chips, or the semiconductor wafer, the ratio of the semiconductor devices having poor connection can be reduced.
The raw material of the uniform joining sheet is not particularly limited, and examples thereof include: polytetrafluoroethylene resin, polyimide resin, phenoxy resin, epoxy resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyether sulphone resin, polyetherimide resin, polyvinyl acetal resin, urethane resin, and acrylic rubber. From the viewpoint of excellent heat resistance and film-forming properties, the unified bonding sheet may be a sheet containing at least one resin selected from the group consisting of polytetrafluoroethylene resins, polyimide resins, epoxy resins, phenoxy resins, acrylic rubbers, cyanate ester resins, and polycarbodiimide resins. From the viewpoint of particularly excellent heat resistance and film-forming properties, the resin of the unified bonding sheet may be a sheet containing at least one resin selected from the group consisting of polytetrafluoroethylene resins, polyimide resins, phenoxy resins, acrylic resins, and acrylic rubbers. These resins can be used singly or in combination of two or more.
(third method)
The laminate is heated in a heating furnace or on a heating plate to a temperature not lower than at least one of the melting point of the metal material forming the surface of the connection portion of the semiconductor chip or the melting point of the metal material forming the surface of the connection portion of the substrate or another semiconductor chip.
In the case of the above method, the time required for heating and cooling the pressing member for temporary pressure bonding can be shortened by performing the temporary pressure bonding step and the main pressure bonding step separately. Therefore, the semiconductor device can be manufactured in a shorter time and with good productivity than when pressure bonding is performed using one pressure bonding pressing member. As a result, a large number of highly reliable semiconductor devices can be manufactured in a short time. In the above method, the plurality of stacked bodies may be heated collectively in a heating furnace or on a hot plate. This enables the semiconductor device to be manufactured with higher productivity.
Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.
Examples
The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
< production of film-like adhesive with base Material >
2.4g of a polyfunctional solid Epoxy resin having a triphenol methane skeleton (manufactured by Japan Epoxy Resins co., ltd., trade name "EP 1032H 60"), 0.45g of a bisphenol F type liquid Epoxy resin (manufactured by Japan Epoxy Resins co., ltd., trade name "YL 983U"), and 0.15g of a flexible Epoxy resin (manufactured by Japan Epoxy Resins co., ltd., trade name "YL 7175") were loaded as Epoxy Resins; 0.1g of 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct (manufactured by SHIKOKU CHEMICALS CORPORATION, trade name "2 MAOK-PW") as a curing agent; 0.1g (0.69mmol) of 2-methylglutaric acid as a flux; silica filler (manufactured by Admatechs co., ltd., trade name "SE 2050", average particle diameter 0.5 μm)0.38g, epoxy silane-treated silica filler (manufactured by Admatechs co., ltd., trade name "SE 2050-SEJ", average particle diameter 0.5 μm)0.38g, and acrylic surface-treated nano-silica filler (manufactured by Admatechs co., ltd., trade name "YA 050C-SM", average particle diameter about 50nm)1.14g as inorganic filler; 0.25g of an organic filler (trade name "EXL-2655", core-shell type organic fine particles, manufactured by Rohm and Haas Japan co., ltd.); and methyl ethyl ketone (such that the amount of solid content became 63 mass%), and zirconia beads having a diameter of 0.8mm and zirconia beads having a diameter of 2.0mm, which were the same mass as the solid content, were added thereto, and stirred for 30 minutes by a bead mill (Fritsch Japan Co., Ltd., planetary micro mill P-7). Then, 1.7g of a phenoxy resin (trade name "ZX 1356-2", Tg: about 71 ℃ C., Mw: about 63000, manufactured by Tokyo chemical Co., Ltd.) was added thereto, and after stirring again for 30 minutes by means of a bead mill, zirconia beads used for the stirring were removed by filtration to obtain a resin varnish.
The obtained resin varnish was coated on a supporting substrate (manufactured by Teijin Dupont Film Japan Limited, trade name "Purex A53") using a small precision coating apparatus (Yasui Seiki), and dried (70 ℃/10min) using a clean oven (manufactured by ESPEC CORP.), thereby forming an adhesive layer (Film-like adhesive) having a thickness of 16 μm. In this way, a film-like adhesive with a base material, which is composed of a support base material and an adhesive layer, is obtained.
< production of Back-side grinding tape (UV-curable type) >
1000g of ethyl acetate, 650g of 2-ethylhexyl acrylate, 350g of 2-hydroxyethyl acrylate and 3.0g of azobisisobutyronitrile were mixed in a 4000mL autoclave equipped with a three-one motor, a stirring blade and a nitrogen introduction tube, and stirred until uniform. Then, bubbling was performed at a flow rate of 100mL/min for 60 minutes to degas the dissolved oxygen in the system. The temperature was raised to 60 ℃ over 1 hour, and polymerization was carried out for 4 hours after the temperature rise. Then, the temperature was raised to 90 ℃ over 1 hour, and further, the temperature was maintained at 90 ℃ for 1 hour, followed by cooling to room temperature.
Subsequently, 1000g of ethyl acetate was added to the autoclave, and the mixture was diluted with stirring. To this mixture, 0.1g of methoxyphenol as a polymerization inhibitor and 0.05g of dioctyltin dilaurate as a urethane formation catalyst were added, 100g of 2-methacryloyloxyethyl isocyanate (product name "Karenz MOI" manufactured by SHOWA DENKO k.k.) was added, and the mixture was reacted at 70 ℃ for 6 hours, followed by cooling to room temperature. Then, ethyl acetate was added thereto to adjust the nonvolatile content of the acrylic resin solution to 35% by mass, thereby obtaining an acrylic resin solution having a functional group capable of chain polymerization. The obtained resin had a hydroxyl value of 121 mgKOH/g. GPC measurement was carried out using SD-8022/DP-8020/RI-8020 manufactured by TOSOH CORPORATION, Gelpack GL-A150-S/GL-A160-S manufactured by Hitachi Chemical Co., Ltd., in a column, and tetrahydrofuran in an eluent, and as a result, the weight average molecular weight in terms of polystyrene was 42 ten thousand.
100g of the acrylic resin solution having chain polymerizable double bonds obtained by the above method as a solid content, 12.0g of polyfunctional isocyanate (product name "Coronate L" manufactured by Nippon Polyurethane Industry co., ltd., product name "Irgacure 184") as a crosslinking agent as a solid content, 1.0g of 1-hydroxycyclohexyl phenyl ketone (product name "Irgacure 184" manufactured by Ciba Specialty Chemicals inc., product name) as a photopolymerization initiator, and ethyl acetate were added so that the total solid content became 27 mass%, and the mixture was uniformly stirred for 10 minutes to obtain a varnish for a pressure-sensitive adhesive layer.
The above adhesive varnish was applied to a polyethylene terephthalate substrate (manufactured by UNITIKA ltd., trade name "embed S25") having a thickness of 25 μm by using an applicator while adjusting the gap so that the thickness of the pressure-sensitive adhesive layer after drying became 50 μm, and dried at 80 ℃ for 5 minutes. Thus, a back grinding tape in which a UV-curable pressure-sensitive adhesive layer was formed on a base material was obtained.
< production of Back-side grinding tape (pressure-sensitive type) >
An acrylic copolymer using 2-ethylhexyl acrylate and methyl methacrylate as main monomers and hydroxyethyl acrylate and acrylic acid as functional group monomers was obtained by a solution polymerization method. The weight average molecular weight of the acrylic copolymer synthesized was 40 ten thousand, and the glass transition point was-38 ℃. To 100 parts by mass of the acrylic copolymer, 10 parts by mass of a polyfunctional isocyanate crosslinking agent (product name "crohnate HL", manufactured by nippon polyurethane industries ltd.) was added to prepare a varnish for pressure-sensitive adhesive.
The above adhesive varnish was applied to a polyethylene terephthalate (PET) substrate (manufactured by UNITIKA LTD., trade name "Emblet S25") having a thickness of 25 μm or 50 μm by means of an applicator while adjusting the gap so that the thickness of the pressure-sensitive adhesive layer after drying became 20 μm, 30 μm, 40 μm or 60 μm, and dried at 80 ℃ for 5 minutes. Thus, a back grinding tape having a pressure-sensitive adhesive layer of pressure-sensitive type formed on a base material was obtained.
< production of adhesive film for semiconductor wafer processing >
(example 1)
The UV-curable back-grinding tape and the film-like adhesive of the tape base were laminated using a roll laminator (lamination temperature: 30 ℃ ± 10 ℃) to obtain an adhesive film for semiconductor wafer processing having a laminated structure of a PET base/pressure-sensitive adhesive layer/supporting base.
(example 2 and comparative examples 1 to 3)
The pressure-sensitive back grinding tape having the thickness of the PET substrate and the pressure-sensitive adhesive layer shown in table 1 and the film-like adhesive with the substrate were laminated using a roll laminator (lamination temperature: 55 ℃ ± 10 ℃) to obtain an adhesive film for semiconductor wafer processing having a laminated structure of PET substrate/pressure-sensitive adhesive layer/supporting substrate.
(measurement of modulus of elasticity)
Test samples were obtained by cutting the back-grinding tapes used in the examples and comparative examples to predetermined dimensions (40 mm in length × 4.0mm in width, thickness being the thickness of each back-grinding tape). For the above test samples, the elastic modulus (storage modulus) at 35 ℃ was measured using a dynamic viscoelasticity measuring apparatus. The details of the method for measuring the elastic modulus are as follows. The measurement results are shown in table 1. Although the elastic modulus was not measured in comparative example 3, the elastic modulus was considered to be higher than those of comparative examples 1 to 2 because the PET substrate was thicker and the pressure-sensitive adhesive layer was thinner than those of comparative examples 1 to 2.
Device name: dynamic viscoelasticity measuring apparatus (UBM co., ltd. manufactured, Rheogel-E4000)
Measurement temperature region: 30 ℃ to 270 DEG C
Temperature rise rate: 5 ℃/min
Frequency: 10Hz
Strain: 0.05 percent
Measurement mode: stretching mode
(evaluation of laminating Property)
As an embedding evaluation wafer for laminating an adhesive film for processing a semiconductor wafer, a 12-inch silicon wafer was prepared in which a plurality of grooves having a depth of 10 μm were formed at a pitch of 10mm in the vertical and horizontal directions.
The adhesive films for processing semiconductor wafers obtained in the examples and comparative examples were laminated onto the 12-inch silicon wafer from the side of the adhesive layer exposed by peeling off the support base material using a vacuum laminator V130 (manufactured by nichogo-Morton co., ltd.), and it was confirmed whether or not voids remained in the grooves. The lamination conditions were 80 ℃ for lamination temperature, 0.5MPa for lamination pressure, and 60 seconds for lamination time. As a result of observation of the groove portion after lamination, a case where lamination was possible without voids left was evaluated as "a", and a case where voids were left was evaluated as "B". The results are shown in table 1.
[ Table 1]
Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3
Thickness of PET substrate (μm) 25 25 25 25 50
Thickness of pressure sensitive adhesive layer (μm) 50 60 30 40 20
Total thickness of BG tape (μm) 75 85 55 65 70
Curing type of pressure-sensitive adhesive layer UV curing Pressure sensitive Pressure sensitive Pressure sensitive Pressure sensitive
BG band elastic modulus (GPa) at 35 DEG C 1.5 1.4 2.5 1.9 -
Thickness of adhesive layer (μm) 16 16 16 16 16
Thickness ratio of pressure-sensitive adhesive layer/adhesive layer 3.1 3.8 1.9 2.5 1.3
Lamination property A A B B B
As is clear from the results shown in table 1, it was confirmed that when the adhesive films for semiconductor wafer processing of examples 1 and 2 were laminated on a wafer, generation of voids could be suppressed even when the wafer had grooves. In addition, in this method, since the generation of voids can be suppressed without changing the composition of the adhesive layer and the lamination conditions, the fillet and the wafer warpage are not adversely affected, and these problems do not actually occur in embodiment 1 and embodiment 2.
Industrial applicability
According to the method for manufacturing a semiconductor device and the adhesive film for processing a semiconductor wafer of the present invention, even when the film-like adhesive is thinned for the purpose of suppressing fillet, generation of voids at the time of laminating wafers can be suppressed. Therefore, according to the method for manufacturing a semiconductor device and the adhesive film for processing a semiconductor wafer of the present invention, it is possible to manufacture a semiconductor device in which generation of voids is suppressed.
Description of the symbols
1-supporting substrate, 2-film-like adhesive (adhesive layer), 3-pressure-sensitive adhesive layer, 4-substrate, 5-back-grinding tape, 6-dicing tape, 7-wired circuit board, 10-adhesive film for semiconductor wafer processing, 20-semiconductor wafer, 20 a-semiconductor chip, 22-bump, 24-solder ball, 26-solder bump (bump electrode), 28-groove, 36-electrode, 100-semiconductor device.

Claims (9)

1. A method for manufacturing a semiconductor device, comprising: preparing a semiconductor wafer having a plurality of electrodes on one main surface thereof, and attaching a semiconductor wafer processing adhesive film including a base material, a back-grinding tape including a pressure-sensitive adhesive layer formed on the base material, and an adhesive layer formed on the pressure-sensitive adhesive layer, to the side of the semiconductor wafer on which the electrodes are provided, from the adhesive layer side, to obtain a laminate;
grinding a side of the semiconductor wafer opposite to a side on which the electrode is provided to reduce a thickness of the semiconductor wafer;
dicing the semiconductor wafer having a reduced thickness and the adhesive layer into individual semiconductor chips having an adhesive layer; and
a step of electrically connecting the electrode of the semiconductor chip with the adhesive layer to an electrode of another semiconductor chip or a printed circuit board,
the thickness of the back grinding belt is 75-300 μm,
the thickness of the pressure-sensitive adhesive layer is more than 3 times of the thickness of the adhesive layer.
2. The manufacturing method according to claim 1,
the back surface polishing tape has an elastic modulus at 35 ℃ of 1.5GPa or less.
3. The manufacturing method according to claim 1 or 2,
the substrate is a polyethylene terephthalate film.
4. The manufacturing method according to any one of claims 1 to 3,
the adhesive force between the pressure sensitive adhesive layer and the adhesive layer is lower than the adhesive force between the adhesive layer and the semiconductor wafer.
5. The manufacturing method according to any one of claims 1 to 4,
the thickness of the adhesive layer is less than the height of the electrodes of the semiconductor wafer.
6. The manufacturing method according to any one of claims 1 to 5,
the semiconductor wafer has a groove in a main surface having the electrode.
7. An adhesive film for processing a semiconductor wafer, comprising:
the back grinding belt comprises a base material and a pressure-sensitive adhesive layer formed on the base material; and
an adhesive layer formed on the pressure-sensitive adhesive layer,
the thickness of the back grinding belt is 75-300 μm,
the thickness of the pressure-sensitive adhesive layer is more than 3 times of the thickness of the adhesive layer.
8. The adhesive film for semiconductor wafer processing according to claim 7, wherein,
the back surface polishing tape has an elastic modulus at 35 ℃ of 1.5GPa or less.
9. The adhesive film for semiconductor wafer processing according to claim 7 or 8, wherein,
the substrate is a polyethylene terephthalate film.
CN201980070581.7A 2018-11-12 2019-11-06 Method for manufacturing semiconductor device and adhesive film for processing semiconductor wafer Pending CN112930584A (en)

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