CN113206039A - Protective film forming film, composite sheet for forming protective film, and method for manufacturing device - Google Patents
Protective film forming film, composite sheet for forming protective film, and method for manufacturing device Download PDFInfo
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- CN113206039A CN113206039A CN202110047614.5A CN202110047614A CN113206039A CN 113206039 A CN113206039 A CN 113206039A CN 202110047614 A CN202110047614 A CN 202110047614A CN 113206039 A CN113206039 A CN 113206039A
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- Prior art keywords
- protective film
- film
- forming
- film forming
- protective
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Images
Classifications
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- 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
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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
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/52—Mounting semiconductor bodies in containers
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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- 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
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/544—Marks applied to semiconductor devices or parts, e.g. registration marks, alignment structures, wafer maps
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
Landscapes
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dicing (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Laser Beam Processing (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a protective film forming film and a protective film forming composite sheet, and a method for using the protective film forming composite sheet manufacturing device, wherein the protective film forming film and the protective film forming composite sheet can improve the adhesion reliability between sealing resin and protective film even if a workpiece such as a chip with the protective film is further sealed by resin. The protective film forming film is a protective film forming film for forming a protective film, and the surface roughness Ra1 of the protective film after heating at 260 ℃ for 5 minutes is 200nm or less.
Description
Technical Field
The present invention relates to a method for manufacturing a protective film forming film, a protective film forming composite sheet, and a device. In particular, the present invention relates to a protective film forming film suitable for protecting a workpiece such as a wafer or a workpiece such as a chip, a composite sheet for forming a protective film including the protective film forming film, and a method for manufacturing an apparatus using the protective film forming film.
Background
In recent years, a semiconductor device is manufactured by a mounting method called flip chip bonding (flip chip bonding). In this mounting method, when a semiconductor chip having a circuit surface on which electrodes such as bumps (bumps) are formed is mounted, the circuit surface side of the semiconductor chip is inverted (face down) and connected to a chip mounting portion. Therefore, the semiconductor device has a structure in which the back surface side of the semiconductor chip on which no circuit is formed is exposed.
Therefore, in order to protect the semiconductor chip from impact during transportation or the like, a hard protective film made of an organic material is often formed on the back surface side of the semiconductor chip. Patent document 1 discloses that the protective film is laser-marked, and the contrast between the marked portion after the laser marking and the portion other than the marked portion is 20% or more.
However, from the viewpoint of miniaturization and high-density mounting of semiconductor packages, wafers for wafer-level chip scale packages (WLCSP) on which circuits, electrodes, and the like are formed are singulated (singulated) to produce WLCSP as chips. The chip has a protective film formed on the surface where the electrodes and the like are not formed, the protective film having the same shape as the chip.
In recent years, System In Package (SiP) in which a plurality of chips having different functions are arranged in one package has been used to achieve both miniaturization and high functionality of a semiconductor package.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012 and 028396
Disclosure of Invention
Technical problem to be solved by the invention
When a chip with a protective film (e.g., a WLCSP with a protective film) is mounted in a system-in-package, the chip with the protective film is sealed so that the protective film exposed to the outside is covered with a sealing resin.
In such a system-in-package in which a chip with a protective film (for example, WLCSP with a protective film) is sealed, there is a problem that peeling occurs between a sealing resin and a protective film in a reliability test, and adhesiveness is lowered.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a protective film forming film and a protective film forming composite sheet which can improve the adhesion reliability between a sealing resin and a protective film even when a work such as a chip on which the protective film is formed is further sealed with the resin, and a method for manufacturing an apparatus using the protective film forming composite sheet.
Means for solving the problems
The present invention relates to the following aspects.
[1] A protective film forming film for forming a protective film, wherein the surface roughness Ra1 of the protective film after heating at 260 ℃ for 5 minutes is 200nm or less.
[2] The protective film forming film according to [1], wherein a water contact angle of the protective film is 107 ° or less.
[3] The protective film forming film according to [1] or [2], wherein the surface roughness Ra0 of the protective film before heating at 260 ℃ for 5 minutes is 35nm or more.
[4] The protective film forming film according to any one of [1] to [3], wherein the protective film is a heat-cured product or an energy ray-cured product.
[5] The protective film forming film according to any one of [1] to [4], wherein the protective film contains a filler.
[6] The protective film forming film according to [5], wherein the filler is composed of two or more fillers having different average particle diameters.
[7] A composite sheet for forming a protective film, which comprises the protective film forming film according to any one of [1] to [6] laminated on a support sheet.
[8] A method of manufacturing a device, comprising:
a step of attaching the protective film-forming film of any one of [1] to [6] or the protective film-forming film of the composite sheet for forming a protective film of [7] to the back surface of a workpiece;
a step of forming a protective film by forming the attached protective film into a protective film;
singulating the workpiece having the protective film or the protective film forming film on the back surface thereof into individual pieces to obtain a plurality of processed products of the workpiece having the protective film or the protective film forming film;
disposing a work piece with a protective film or a protective film forming film on a substrate; and
and heating the processed product of the workpiece with the protective film arranged on the substrate and the substrate.
[9] A method of manufacturing a device, comprising:
a step of attaching the protective film-forming film of any one of [1] to [6] or the protective film-forming film of the composite sheet for forming a protective film of [7] to the back surface of a workpiece;
a step of forming a protective film by forming the attached protective film into a protective film;
a step of laser marking the protective film or the protective film forming film so that the height of the printed portion is greater than 0 [ mu ] m;
singulating the workpiece having the protective film or the protective film forming film on the back surface thereof into individual pieces to obtain a plurality of processed products of the workpiece having the protective film or the protective film forming film;
disposing a work piece with a protective film or a protective film forming film on a substrate; and
and heating the processed product of the workpiece with the protective film arranged on the substrate and the substrate.
[10] A method for manufacturing a device, wherein the step of heating the work with the protective film and the substrate arranged on the substrate described in [8] or [9], is followed by a sealing treatment step of covering the protective film exposed to the work with the protective film with a sealing resin.
[11] The method of manufacturing a device according to any one of [8] to [10], wherein the workpiece is a wafer, and the workpiece to be processed is a chip.
Effects of the invention
According to the present invention, it is possible to provide a protective film forming film and a protective film forming composite sheet, which can improve the adhesion reliability between a sealing resin and a protective film even when a work such as a chip on which the protective film is formed is further sealed with a resin, and a method for manufacturing an apparatus using the protective film forming composite sheet.
Drawings
Fig. 1 is a schematic cross-sectional view of an example of a chip having a protective film obtained by forming a protective film forming film of the present embodiment into a protective film.
Fig. 2 is a schematic cross-sectional view of an example of the composite sheet for forming a protective film according to the present embodiment.
Fig. 3 is a schematic cross-sectional view of another example of the composite sheet for forming a protective film according to the present embodiment.
Fig. 4 is a schematic cross-sectional view for explaining a step of attaching the composite sheet for forming a protective film of the present embodiment to a wafer.
Fig. 5 is a schematic cross-sectional view for explaining a step of singulating the wafer on which the protective film is formed.
Fig. 6 is a schematic cross-sectional view for explaining a process of picking up a chip on which a protective film is formed.
Fig. 7 is a schematic cross-sectional view for explaining a process of disposing a chip on a substrate, the chip having a protective film formed thereon.
Fig. 8 is a schematic sectional view showing a substrate provided with a chip on which a protective film is formed and other chips.
Fig. 9 is a schematic cross-sectional view showing a system in package obtained by sealing a chip mounted on a substrate and having a protective film formed thereon with a sealing resin.
Description of the reference numerals
10: a chip with a protective film; 1: forming a film by the protective film; 1 a: a protective film; 6 a: a chip; 6 b: a convex electrode; 3. 3A: a composite sheet for forming a protective film; 1: forming a film by the protective film; 4: an adhesive sheet; 41: a substrate; 42: an adhesive layer; 5: an adhesive layer for a jig; 6: a wafer; 7: an annular frame; 50: a substrate; 100: and (4) system-in-package.
Detailed Description
First, main terms used in the present specification will be described.
In the present specification, "(meth) acrylate" is used as a term indicating both "acrylate" and "methacrylate", and other similar terms are also used.
The support sheet refers to a sheet supporting the protective film to form a film. As the support sheet, an adhesive sheet, which is a laminate including a base material and an adhesive layer, or only a base material may be illustrated. In this embodiment, the supporting sheet is preferably an adhesive sheet in view of easy control of adhesion to the protective film forming film and the protective film, and in view of easy control of Ra0 which is also advantageous in surface roughness Ra1 of the protective film to be described later.
The adhesive sheet may contain other structural layers than the base material and the adhesive layer. For example, the adhesive sheet may have a structure including an intermediate layer between the substrate and the adhesive layer. In addition, for the purpose of improving adhesion at the interface between the substrate surface and the adhesive agent layer or at the interface between the substrate surface and the intermediate layer, preventing transfer of low molecular weight components, and the like, an undercoat layer (primer layer) may be formed on the substrate surface on the adhesive agent layer side. Further, a release film for protecting the adhesive layer before use may be laminated on the surface of the adhesive layer. The substrate may be a single layer or may be a multilayer having a functional layer such as a buffer layer.
The "front surface" of a workpiece such as a wafer refers to a surface on which circuits, electrodes, and the like are formed, and the "back surface" refers to a surface on which no circuits and the like are formed.
Hereinafter, the present invention will be described in detail by the following procedure with reference to specific embodiments.
(1. protective film forming film)
The protective film forming film of the present embodiment is formed into a protective film by being attached to a workpiece and formed into a protective film, thereby forming a protective film for protecting the workpiece or a workpiece to be processed.
The "protective film formation" refers to a state in which a protective film is formed to have sufficient characteristics for protecting a workpiece or a processed article of the workpiece. Specifically, when the protective film forming film of the present embodiment is curable, "forming a protective film" means forming an uncured protective film forming film into a cured product. In other words, the protective film formed into a protective film is a cured product of the protective film forming film, and is different from the protective film forming film.
After the work and the curable protective film forming film are superposed on each other, the protective film can be firmly bonded to the work by curing the protective film forming film, and a durable protective film can be formed.
On the other hand, when the protective film forming film of the present embodiment is used in a non-cured state without containing a curable component, the protective film forming film of the present embodiment is formed into a protective film at the moment when the protective film forming film is attached to a workpiece. In other words, the protective film forming film formed as the protective film is the same as the protective film forming film.
When high protective performance is not required, the protective film-forming film is easy to use because it is not necessary to cure the protective film-forming film.
In the present embodiment, the protective film forming film is preferably curable. Therefore, the protective film is preferably a cured product. Examples of the cured product include a thermal cured product and an energy ray cured product. In the present embodiment, the protective film is more preferably a thermal cured product.
The protective film forming film preferably has adhesiveness at normal temperature (23 ℃) or exhibits adhesiveness by heating. Thus, when the work and the protective film forming film are superposed, the work and the protective film forming film can be bonded to each other. Therefore, positioning can be reliably performed before the protective film forming film is cured.
The work is a plate-like body to which the protective film forming film of the present embodiment is attached and processed. Examples of the work include a wafer and a panel (panel). Specifically, a semiconductor wafer and a semiconductor panel are exemplified. As the processed product of the workpiece, for example, a wafer is singulated to obtain chips. Specifically, a semiconductor wafer is singulated to obtain semiconductor chips. At this time, a protective film is formed on the back surface side of the wafer.
The protective film forming film may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the protective film forming film has a plurality of layers, these plurality of layers may be the same as or different from each other, and the combination of the layers constituting these plurality of layers is not particularly limited.
In the present embodiment, the protective film forming film is preferably one layer (single layer). If the protective film forming film is composed of multiple layers, there is a risk that: in the step of generating a temperature change (at the time of reflow treatment or at the time of using a device), interlayer peeling or film deformation occurs due to a difference in interlayer heat shrinkability, and this film deformation also involves a change in the surface roughness Ra 1. However, if the protective film forming film is composed of one layer, this risk can be reduced.
The thickness of the protective film-forming film is not particularly limited, but is preferably 5 μm to 100 μm, 7 μm to 50 μm, 9 μm to 30 μm, 11 μm to 30 μm, 13 μm to 25 μm, or 14 μm to 24 μm.
By setting the thickness within the above range, the movement of the material in the protective film in the thickness direction is suppressed, the desired surface roughness Ra0 and Ra1 of the protective film is easily obtained, and adverse effects such as the displacement of the chip with the protective film due to the pressure of the flow of the sealing resin are not easily generated when the sealing treatment is performed.
The thickness of the protective film forming film is the thickness of the entire protective film forming film. For example, the thickness of the protective film forming film composed of a plurality of layers means the total thickness of all the layers constituting the protective film forming film.
Hereinafter, a protective film formed on a chip as a work of a workpiece will be described. Specifically, a protective film formed by forming a protective film forming film into a protective film according to the present embodiment will be described using the chip 10 with a protective film shown in fig. 1.
As shown in fig. 1, the chip with a protective film 10 has a protective film 1a formed on the back surface side (upper side in fig. 1) of the chip 6a, and a convex electrode 6b formed on the front surface side (lower side in fig. 1) of the chip 6 a.
A circuit is formed on the front surface side of the chip 6a, and the convex electrode 6b is formed to be electrically connected to the circuit. As will be described in detail later, the chip 10 with a protective film is disposed so that the surface on which the convex electrode 6b is formed faces the chip mounting substrate. Then, the substrate is mounted through the convex electrode 6b by electrical and mechanical connection through a predetermined heating process (reflow process). The convex electrode 6b may be a bump or a columnar electrode.
(1.1 surface roughness of protective film)
In this embodiment, after the protective film 1a shown in fig. 1 is heated at 260 ℃ for 5 minutes, the roughness of the surface S of the protective film 1a is 200nm or less. The surface roughness is expressed as an arithmetic average roughness Ra. In the present embodiment, the surface roughness of the surface S of the protective film 1a after heating at 260 ℃ for 5 minutes is represented as Ra 1. Namely, Ra1 is 200nm or less.
The treatment of heating at 260 ℃ for 5 minutes is assumed to be a heating treatment performed when the chip 10 with the protective film is mounted on the chip mounting substrate. After the heat treatment, the chip 10 with the protective film may be sealed with a resin. This sealing process is performed, for example, when manufacturing a System In Package (SiP) in which a plurality of chips are sealed in one package.
By setting the roughness Ra1 of the surface S of the protective film 1a after heating at 260 ℃ for 5 minutes to 200nm or less, the adhesion reliability between the protective film and the sealing resin for sealing the chip 10 with the tape protective film is improved.
The reason for the improvement of the adhesion reliability is not clear, but is presumed to be, for example, as follows: the treatment of heating at 260 ℃ for 5 minutes affects the compatibility of the components contained in the protective film and also affects the fluidity of the components contained in the protective film. Therefore, the surface roughness of the protective film after heating at 260 ℃ for 5 minutes was changed from that before heating. When the surface roughness Ra1 is larger than the above range, the surface of the protective film is not smooth, and therefore the sealing resin cannot sufficiently enter the unevenness of the protective film, and the protective film cannot sufficiently embed in the sealing resin. As a result, voids are generated at the interface of the protective film and the sealing resin. Air or water may be present at the gap. When the package is heated in a state where a void exists, the protective film and the sealing resin are peeled off from each other from the void due to expansion of air or water vapor. Therefore, there is a tendency that the adhesion reliability between the protective film and the sealing resin is lowered.
Further, the following effects can be expected by setting the surface roughness Ra1 to 200nm or less.
In WLCSP and the like, a convex electrode such as a bump is disposed on the lower surface of a package and is connected to a substrate when mounted. Therefore, even if the inspection is performed using an optical system from the protective film side, it is difficult to detect a connection failure (disconnection, short circuit, or the like) with the substrate. In an inspection using a transmission X-ray apparatus, although a short-circuit failure can be detected, an unconnected failure cannot be detected.
Therefore, for example, a tomography (tomography) method or a tomosynthesis (tomosynthesis) method, which is a three-dimensional inspection method using X-rays, may be used to detect both types of connection failures. In the inspection method using X-rays, the smaller the surface roughness of the protective film irradiated with X-rays, the more accurately the connection failure can be detected. Therefore, from the viewpoint of detecting a connection failure, it is also preferable that the surface roughness Ra1 be 200nm or less.
The surface roughness Ra1 is preferably 150nm or less, 125nm or less, 100nm or less, 80nm or less, or 60nm or less.
On the other hand, the surface roughness Ra1 is preferably 35nm or more, 40nm or more, and 45nm or more. By setting the lower limit value of Ra1 to the above value, the surface of the protective film is moderately rough, so that an anchoring effect (anchoring effect) of the sealing resin can be obtained, and good adhesion reliability can be easily obtained.
In the present embodiment, the surface roughness of the surface S of the protective film 1a before heating at 260 ℃ for 5 minutes is preferably 35nm or more. The surface roughness is expressed as arithmetic mean roughness Ra. In the present embodiment, the surface roughness of the surface S of the protective film 1a before heating at 260 ℃ for 5 minutes is represented as Ra 0. That is, Ra0 is preferably 35nm or more.
Ra0 is assumed as the surface roughness of the protective film before reflow soldering. The chip 10 with the protective film is placed on a predetermined terminal portion of the chip mounting board and then subjected to reflow soldering. As a method of disposing the chip 10 with the protective film on the chip mounting substrate, for example, a method of sucking the chip 10 with the protective film stored on a tray, a tape, or the like by using a suction nozzle and separating the chip 10 with the protective film at a predetermined position on the chip mounting substrate may be cited. In this method, the surface S of the protective film is sucked and detached by the suction nozzle. At this time, if the surface S of the protective film has a certain degree of roughness, the protective film can be smoothly detached from the suction nozzle without causing positional deviation or the like. Therefore, when Ra0 is within the above range, the chip 10 with the protective film is reliably disposed on the chip mounting board, and the mounting failure is reduced.
The surface roughness Ra0 is preferably 35nm or more, more preferably 40nm or more, and still more preferably 45nm or more.
(1.2 Water contact Angle)
In the present embodiment, the water contact angle of the surface S of the protective film 1a after heating at 260 ℃ for 5 minutes is preferably 107 ° or less. That is, the surface S of the protective film 1a is preferably highly wettable after being heated at 260 ℃ for 5 minutes. When the water contact angle of the surface S is 107 ° or less, the adhesion reliability between the protective film and the sealing resin tends to be improved.
The water contact angle is more preferably 105 ° or less, still more preferably 102 ° or less, and particularly preferably 100 ° or less.
The water contact angle also changes depending on the surface roughness Ra1, and also changes depending on other surface conditions (polarity, etc.).
(1.3 composition for Forming protective film)
The composition of the protective film forming film is not particularly limited as long as the protective film has the above physical properties. In the present embodiment, the composition constituting the protective film forming film (protective film forming composition) is preferably a resin composition containing at least the polymer component (a), the curable component (B), and the filler (E). The polymer component can be considered as a component formed by a polymerization reaction of a polymerizable compound. The curable component is a component capable of undergoing a curing (polymerization) reaction. In the present specification, the polymerization reaction also includes a polycondensation reaction.
Further, a component contained in the polymer component may be a curable component. In the present embodiment, when the composition for forming a protective film contains two components belonging to the polymer component and the curable component, the composition for forming a protective film is considered to contain the polymer component and the curable component.
(1.3.1 Polymer component)
The polymer component (a) imparts appropriate tackiness to the protective film-forming film while imparting film formability (film formability), thereby reliably and uniformly adhering the protective film-forming film to the work. The weight average molecular weight of the polymer component is usually in the range of 5 to 200 ten thousand, preferably in the range of 10 to 150 ten thousand, and particularly preferably in the range of 20 to 100 ten thousand. If the weight average molecular weight is too small, the movement of the material in the protective film, which roughens the surface of the protective film, cannot be suppressed when the film is heated at 260 ℃. On the other hand, if the weight average molecular weight is too large, compatibility with other components is deteriorated, and as a result, formation of a uniform film is inhibited. As such a polymer component, for example, an acrylic resin, a urethane resin, a phenoxy resin, a silicone resin, a saturated polyester resin, or the like can be used, and an acrylic resin is particularly preferably used.
In the present specification, unless otherwise specified, "weight average molecular weight" refers to a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC).
Examples of the acrylic resin include (meth) acrylate copolymers composed of structural units derived from a (meth) acrylate monomer and a (meth) acrylic acid derivative. The (meth) acrylate monomer is preferably an alkyl (meth) acrylate having an alkyl group with 1 to 18 carbon atoms, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
In the present embodiment, it is preferable to introduce a glycidyl group into the acrylic resin by glycidyl (meth) acrylate or the like. The acrylic resin having a glycidyl group introduced therein has improved compatibility with an epoxy resin as a thermosetting component described later, and the glass transition temperature (Tg) of the protective film forming film after curing is increased, thereby improving heat resistance. In the present embodiment, it is preferable to introduce hydroxyl groups into the acrylic resin by hydroxyethyl acrylate or the like in order to control adhesion to a work and adhesive properties.
The glass transition temperature of the acrylic resin is preferably-70 ℃ to 40 ℃, 40 ℃ to 36 ℃, 30 ℃ to 32 ℃, 20 ℃ to 28 ℃, 10 ℃ to 24 ℃ and 1 ℃ to 20 ℃. By setting the lower limit value of the glass transition temperature of the acrylic resin to the above value, the protective film forming film and the fluidity of the protective film at the time of heating are suppressed, and therefore, the surface roughness of the protective film is easily controlled.
When the acrylic resin has m kinds (m is an integer of 2 or more) of structural units, the glass transition temperature of the acrylic resin can be calculated as follows. That is, when any non-repeating number from 1 to m is assigned to each of the m monomers from which the structural unit in the acrylic resin is derived in order and these are named as "monomers m", the glass transition temperature (Tg) of the acrylic resin can be calculated using the Fox equation shown below.
[ mathematical formula 1]
Wherein Tg is a glass transition temperature of the acrylic resin, m is an integer of 2 or more, Tgk is a glass transition temperature of a homopolymer of monomer m, Wk is a mass fraction of structural unit m derived from monomer m in the acrylic resin, and Wk satisfies the following formula.
[ mathematical formula 2]
Wherein m and Wk are the same as those described above.
As Tgk, values described in a Polymer data manual (polymers データ and ハンドブック), an adhesion manual (adhesion ハンドブック), a Polymer manual (Polymer Handbook), or the like can be used. For example, a homopolymer of methyl acrylate at Tgk ℃ at Tgk ℃ at-54 ℃ and a homopolymer of n-butyl acrylate at Tgk ℃ at 105 ℃ and a homopolymer of 2-hydroxyethyl acrylate at Tgk ℃ at-15 ℃ and a homopolymer of glycidyl methacrylate at Tgk ℃ at 41 ℃ and 2-ethylhexyl acrylate at Tgk ℃ at-70 ℃.
The content of the polymer component is preferably 5 to 80 parts by mass, 6 to 50 parts by mass, 7 to 40 parts by mass, 8 to 35 parts by mass, 9 to 30 parts by mass, or 10 to 25 parts by mass, when the total weight of the protective film forming composition is 100 parts by mass. By setting the upper limit of the content of the polymer component to the above value, the component having high fluidity when heated at 260 ℃ in the composition for forming a protective film is reduced, and therefore, the movement of the material in the protective film, which tends to roughen the surface when heated at 260 ℃, can be suppressed.
(1.3.2 thermosetting Components)
The curable component (B) forms a hard protective film by curing the protective film-forming film. As the curable component, a thermosetting component, an energy ray curable component, or a mixture thereof can be used. When the protective film of this embodiment is cured by irradiation with an energy ray, the light transmittance is reduced because the protective film contains a filler described later. Therefore, for example, when the thickness of the protective film forming film is thick, the energy ray curing is liable to become insufficient.
On the other hand, since the thermosetting protective film-forming film can be sufficiently cured by heating even if it is thick, a protective film having high protective performance can be formed, and movement of materials in the protective film, which tend to roughen the surface when heated at 260 ℃, can be suppressed. Further, by using a common heating means such as a heating oven, the plurality of protective film formation films can be collectively heated and thermally cured.
Therefore, in the present embodiment, it is desirable that the curable component be thermosetting. That is, the protective film forming film of the present embodiment is preferably thermosetting.
Whether or not the protective film forming film is thermosetting can be judged in the following manner. First, a normal temperature (23 ℃) protective film forming film is heated to a temperature higher than the normal temperature, and then cooled to the normal temperature, thereby forming a heated and cooled protective film forming film. Next, the hardness of the protective film forming film after heating and cooling and the hardness of the protective film forming film before heating are compared at the same temperature, and when the protective film forming film after heating and cooling is hard, it is judged that the protective film forming film is thermosetting.
As the thermosetting component, for example, epoxy resin, polyimide resin, unsaturated polyester resin, and a mixture thereof are preferably used.
Epoxy resins, which are thermosetting components, have the property of forming a three-dimensional network when heated, thereby forming a strong film. As such an epoxy resin, various known epoxy resins can be used. In the present embodiment, the molecular weight (formula weight) of the epoxy resin is preferably 300 or more and less than 50000, 300 or more and less than 10000, 300 or more and less than 5000, 300 or more and less than 3000. The epoxy equivalent of the epoxy resin is preferably 50 to 5000g/eq, more preferably 100 to 2000g/eq, and still more preferably 150 to 1000 g/eq.
Specific examples of such epoxy resins include glycidyl ethers of phenols such as bisphenol a, bisphenol F, resorcinol, phenyl novolac (phenyl novolac), cresol novolac (cresol novolac); glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidyl-type or alkylglycidyl-type epoxy resins obtained by replacing an active hydrogen bonded to a nitrogen atom such as aniline isocyanurate with a glycidyl group; examples of the alicyclic epoxy compound include a vinylcyclohexane diepoxide, 3, 4-epoxycyclohexylmethyl-3, 4-bicyclohexane carboxylate, and 2- (3, 4-epoxy) cyclohexyl-5, 5-spiro (3, 4-epoxy) cyclohexane-m-dioxane, which are so-called alicyclic epoxy compounds having an epoxy group introduced therein by, for example, oxidation of a carbon-carbon double bond in the molecule. Epoxy resins having a biphenyl skeleton, a dicyclohexyldiene skeleton, a naphthalene skeleton, or the like may also be used.
Among them, bisphenol-type glycidyl epoxy resins, o-cresol novolac epoxy resins, and phenol novolac epoxy resins are preferably used. These epoxy resins may be used alone or in combination of two or more.
When a thermosetting component is used as the curable component (B), it is preferable to use the curing agent (C) as an auxiliary at the same time. As the curing agent for epoxy resin, a heat-active latent epoxy resin curing agent is preferable. The "thermally active latent epoxy resin curing agent" is a type which hardly reacts with an epoxy resin at normal temperature (23 ℃) but is activated by heating to a certain temperature or higher to react with the epoxy resin. As a method for activating the heat-reactive latent epoxy resin curing agent, there are a method of generating an active species (anion or cation) in a chemical reaction by heating; a method of stably dispersing in an epoxy resin at around normal temperature, but being compatible with the epoxy resin at high temperature, dissolving and initiating a curing reaction; a method of dissolving out a molecular sieve-encapsulated curing agent at a high temperature to initiate a curing reaction; microcapsule-based methods, and the like.
Among the exemplified methods, a method is preferable in which the epoxy resin is stably dispersed in the epoxy resin at around room temperature, but the epoxy resin is compatible with the epoxy resin at high temperature, and the epoxy resin is dissolved and the curing reaction is initiated.
Specific examples of the heat-active latent epoxy resin curing agent include various onium salts, dibasic acid dihydrazide compounds, dicyanodiamide, amine adduct curing agents, high-melting active hydrogen compounds of imidazole compounds, and the like. These thermally active latent epoxy resin curing agents may be used alone or in combination of two or more. In the present embodiment, dicyanodiamine is particularly preferable.
Further, as a curing agent for an epoxy resin, a phenol resin is also preferable. The phenol resin may be, but is not particularly limited to, a condensate of a phenol such as an alkylphenol, a polyphenol, or naphthol, and an aldehyde. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, t-butylphenol novolac resin, dicyclopentadiene cresol resin, poly-p-vinylphenol resin, bisphenol a-type novolac resin, or modified products thereof can be used.
The phenolic hydroxyl groups contained in these phenol resins can be easily subjected to an addition reaction with the epoxy groups of the epoxy resin by heating, and a cured product having high impact resistance can be formed.
The content of the curing agent (C) is preferably 0.1 to 30 parts by mass, 1.0 to 25 parts by mass, 1.5 to 20 parts by mass, 2.0 to 18 parts by mass, 2.5 to 16 parts by mass, 3.0 to 14 parts by mass, or 3.5 to 12 parts by mass, relative to 100 parts by mass of the epoxy resin. By setting the lower limit value of the content of the curing agent (C) to the above value, the network structure of the protective film becomes dense, and therefore, the movement of the material in the protective film, which tends to roughen the surface when heated at 260 ℃, can be suppressed.
When dicyanodiamine is used as the curing agent (C), it is preferable to further use a curing accelerator (D) together. Preferred examples of the curing accelerator include imidazoles (imidazole in which one or more hydrogen atoms are substituted with a group other than a hydrogen atom), such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-dimethyloimidazole, 2-phenyl-4, 5-dimethyloimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among them, 2-phenyl-4-methyl-5-hydroxymethylimidazole is particularly preferable.
The content of the curing accelerator is preferably 0.01 to 30 parts by mass, 0.1 to 25 parts by mass, 1.0 to 20 parts by mass, 1.5 to 18 parts by mass, 2.0 to 16 parts by mass, 2.5 to 14 parts by mass, or 3.0 to 12 parts by mass, relative to 100 parts by mass of the epoxy resin. By setting the lower limit value of the content of the curing accelerator (D) to the above value, the network structure of the protective film becomes dense, and therefore, the movement of the material in the protective film, which tends to roughen the surface when heated at 260 ℃, can be suppressed.
The total content of the thermosetting component and the curing agent is preferably 5 to 80 parts by mass, 6 to 50 parts by mass, 7 to 40 parts by mass, 8 to 35 parts by mass, 9 to 30 parts by mass, or 10 to 25 parts by mass, based on 100 parts by mass of the total weight of the protective film forming composition. When the thermosetting component and the curing agent are blended in such a ratio, an appropriate viscosity is developed before curing, and the bonding operation can be stably performed. Further, by setting the lower limit value of the total content of the thermosetting component and the curing agent to the above value, a protective film excellent in film strength can be obtained after curing, and therefore, movement of materials in the protective film which tend to roughen the surface when heated at 260 ℃.
(1.3.3 energy ray-curable component)
When the curable component is an energy ray-curable component, the energy ray-curable component is preferably uncured, preferably adhesive, and more preferably uncured and adhesive.
The energy ray-curable component is a component that is cured by irradiation with an energy ray, and is also a component for imparting film formability and flexibility to the protective film-forming film.
As the energy ray-curable component, for example, a compound having an energy ray-curable group is preferable. Examples of such a compound include known compounds having an energy ray-curable group.
(1.3.4 Filler)
By incorporating the filler (E) into the protective film forming film, the thermal expansion coefficient of the protective film obtained by forming the protective film into a protective film can be easily adjusted. By making this thermal expansion coefficient close to that of the work or the sealing resin, the adhesion reliability of the package formed with the film formed using the protective film is further improved. In addition, by incorporating the filler (E) into the protective film forming film, a hard protective film can be obtained, and the moisture absorption rate of the protective film can be further reduced, thereby further improving the adhesion reliability of the package.
The filler (E) may be either an organic filler or an inorganic filler, but is preferably an inorganic filler in view of shape stability at high temperatures up to 260 ℃.
Examples of preferable inorganic fillers include powders of silica, alumina, talc, calcium carbonate, red iron oxide, silicon carbide, boron nitride, and the like; forming the inorganic filler materials into spherical beads; surface modifications of these inorganic filler materials; single crystal fibers of these inorganic fillers; glass fibers, and the like. Among them, silica and surface-modified silica are preferable. The surface-modified silica is preferably modified by means of a coupling agent. More preferably surface-modified by a silane coupling agent.
The average particle diameter of the inorganic filler is preferably 0.06 to 10 μm, more preferably 0.1 to 10 μm, and still more preferably 0.3 to 9 μm.
By setting the lower limit of the average particle size of the inorganic filler to the above value, the handling performance of the composition for forming a protective film is good. Therefore, the protective film forming composition and the quality of the protective film forming film are easily stabilized, and the surface roughness Ra0 before heating at 260 ℃. Further, by setting the upper limit value of the average particle diameter of the inorganic filler to the above value, the surface roughness Ra1 after heating at 260 ℃.
In the present specification, unless otherwise specified, the "average particle diameter" refers to a value of the particle diameter (D50) at which the cumulative value is 50% in a particle size distribution curve obtained by a laser diffraction scattering method.
The content of the inorganic filler is preferably 15 to 80 parts by mass, 30 to 76 parts by mass, 40 to 72 parts by mass, 45 to 68 parts by mass, or 50 to 66 parts by mass, based on 100 parts by mass of the total weight of the protective film forming composition.
By setting the lower limit value of the content of the inorganic filler to the above value, the desired surface roughness Ra0 of the protective film is easily obtained. Further, since the protective film-forming composition contains a large amount of a component which hardly changes the shape of the particles themselves when heated at 260 ℃, it is possible to suppress movement of the material in the protective film which tends to roughen the surface when heated at 260 ℃. Further, by setting the upper limit value of the content of the inorganic filler to the above value, the desired surface roughness Ra0 of the protective film is easily obtained, and as a result, the control of Ra1 is also concerned.
Further, the protective film forming film preferably contains two or more kinds of filler. That is, the filler (E) is preferably two or more fillers. The phrase "containing two or more fillers" means that the filler may contain two or more fillers of different materials, or may contain two or more fillers of different average particle diameters.
In the present embodiment, it is preferable to contain two or more types of fillers having different average particle diameters. By incorporating the filler having different average particle diameters into the protective film forming film, the filler having a small average particle diameter can be easily disposed between the gaps of the filler having a large average particle diameter. As a result, while the above-described effects are obtained, it is easy to control the surface roughness Ra of the protective film after heating at 260 ℃ for 5 minutes within the above-described range. Further, the water contact angle of the protective film after heating at 260 ℃ for 5 minutes is easily controlled within the above range.
When two or more fillers having different average particle diameters are contained, the average particle diameter of the filler having the largest average particle diameter is preferably 1.5 to 100 times, more preferably 2 to 20 times, and still more preferably 3 to 18 times the average particle diameter of the filler having the smallest average particle diameter.
In addition, whether the protective film or the protective film forming film contains two or more types of fillers having different average particle diameters can be confirmed by observing the cross section of the protective film or the protective film forming film.
(1.3.5 coupling agent)
The protective film-forming film preferably contains a coupling agent (F). By containing the coupling agent, the adhesion and the adhesion between the protective film and the work can be improved without impairing the heat resistance of the protective film after the protective film forming film is cured, and the water resistance (moisture and heat resistance) can be improved. As the coupling agent, a silane coupling agent is preferable from the viewpoints of versatility and cost advantage, and the viewpoint of controlling the water contact angle within the above range.
Examples of the silane coupling agent include gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropylmethyldiethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma- (methacryloyloxypropyl) trimethoxysilane, gamma-aminopropyltrimethoxysilane, N-6- (aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxypropylmethyldimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-hydroxysilane, gamma-glycidyloxypropyltrimethoxysilane, gamma-hydroxysilane, beta-hydroxysilane, and the like, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane and the like. These silane coupling agents may be used alone or in combination of two or more.
(1.3.6 colorant)
The protective film forming film preferably contains a colorant (G). Thus, since the back surface of the workpiece such as a chip is covered, various electromagnetic waves generated in the electronic device can be shielded, and failure of the workpiece such as a chip can be reduced.
As the colorant (G), known colorants such as inorganic pigments, organic pigments, and organic dyes can be used. In the present embodiment, an inorganic pigment is preferable.
Examples of the inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (indium tin oxide) pigments, ATO (antimony tin oxide) pigments, and the like. Among them, carbon black is particularly preferably used. Electromagnetic waves in a wide wavelength range can be shielded by the carbon black.
The amount of the colorant (particularly carbon black) to be blended in the protective film forming film varies depending on the thickness of the protective film forming film, but when the thickness of the protective film forming film is 20 μm, for example, the amount is preferably 0.05 to 10 mass%, 0.1 to 7 mass%, 0.5 to mass% with respect to the total mass of the protective film forming film.
The average particle diameter of the colorant (particularly carbon black) is preferably 1 to 500nm, particularly preferably 3 to 100nm, and further preferably 5 to 50 nm. If the average particle diameter of the colorant is within the above range, it is easy to control the light transmittance within a desired range.
(1.3.7 other additives)
The protective film forming film composition may contain, for example, a photopolymerization initiator, a crosslinking agent, a plasticizer, an antistatic agent, an antioxidant, a gettering agent (gelling agent), a tackifier, and the like as other additives within a range that does not impair the effects of the present invention.
(2. sheet for Forming protective film)
Before use, the protective film forming film may be protected on one side or both sides by a release film, and may be rolled up and stored in the form of a protective film forming sheet. The release film is peeled off when the film is formed using the protective film.
The release film may have any composition, and examples thereof include a plastic film having a property of releasing the film itself from the protective film forming film, and a film obtained by peeling a plastic film with a peeling agent or the like. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicones, fluorine-based ones, long-chain alkyl-based ones, and the like can be used, and among them, silicones which are inexpensive and can obtain stable performance are preferable. The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.
When the protective film forming film has the release films on both sides thereof, it is preferable to set the peeling force of one release film to be large as a heavy release type release film and set the peeling force of the other release film to be small as a light release type release film.
(3. composite sheet for Forming protective film)
Fig. 2 is a schematic cross-sectional view of an example of the composite sheet for forming a protective film according to the present embodiment. As shown in fig. 2, the composite sheet 3 for forming a protective film of the present embodiment includes: an adhesive sheet 4 in which an adhesive layer 42 is laminated on one surface of a substrate 41, a protective film forming film 1 laminated on the adhesive layer 42 side of the adhesive sheet 4, and an adhesive layer 5 for a jig laminated on the peripheral portion of the protective film forming film 1 on the opposite side of the adhesive sheet 4. The adhesive layer 5 for a jig is a layer for adhering the composite sheet 3 for forming a protective film to a jig such as an annular frame.
The composite sheet 3 for forming a protective film according to the present embodiment is attached to a workpiece to support the workpiece during processing of the workpiece, and forms a protective film on the workpiece or a processed product of the workpiece by forming the protective film into a protective film 1. The protective film may be a non-cured protective film forming film 1, but is preferably constituted by a cured protective film forming film 1.
The composite sheet 3 for forming a protective film according to the present embodiment is used for supporting a wafer as a workpiece during dicing processing and simultaneously forming a protective film on a chip as a processed product obtained by dicing, but is not limited thereto.
(3.1 adhesive sheet)
The adhesive sheet 4 of the composite sheet 3 for forming a protective film of the present embodiment includes a substrate 41 and an adhesive layer 42 laminated on one surface of the substrate 41. Therefore, as described above, the adhesive sheet is a support sheet that supports the protective film forming film.
(3.1.1. base material)
The material of the substrate 41 of the adhesive sheet 4 is not particularly limited as long as it is a sheet suitable for processing a workpiece, for example, dicing and expanding a wafer, and is generally composed of a film (hereinafter referred to as "resin film") mainly composed of a resin material.
Specific examples of the resin film include polyethylene films such as Low Density Polyethylene (LDPE) films, Linear Low Density Polyethylene (LLDPE) films, and High Density Polyethylene (HDPE) films; polyolefin films such as polypropylene films, polybutylene films, polybutadiene films, polymethylpentene films, ethylene-norbornene copolymer films, and norbornene resin films; ethylene copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylate copolymer films; polyvinyl chloride films such as polyvinyl chloride films and vinyl chloride copolymer films; polyester-based films such as polyethylene terephthalate films and polybutylene terephthalate films; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; fluororesin films, and the like. Modified membranes such as crosslinked membranes and ionomer membranes can also be used. The substrate 41 may be a film composed of one of these films, or may be a laminated film obtained by further combining two or more of these films.
Among the above films, polyolefin films are preferable from the viewpoint of environmental safety, cost, and the like, and among them, polypropylene films having excellent heat resistance are preferable. The polypropylene film can impart heat resistance to the base material 41 without impairing the expansion flexibility of the adhesive sheet 41 or the pickup flexibility of a work such as a chip. Since the base material 41 has such heat resistance, even when the protective film forming film 1 is thermally cured in a state where the composite sheet 3 for protective film formation is attached to a workpiece, the occurrence of slack in the adhesive sheet 4 can be suppressed. Further, the surface roughness Ra0 of the protective film was easily controlled through the adhesive layer, and as a result, Ra1 was also controlled.
In order to improve the adhesion between the resin film and the adhesive layer 42 laminated on the surface thereof, one surface or both surfaces of the resin film may be subjected to surface treatment by an oxidation method or an embossing method, or primer treatment, as necessary. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet type), flame treatment, hot air treatment, ozone treatment, and ultraviolet irradiation treatment, and examples of the roughening method include sand blast treatment and thermal spray treatment.
The resin film may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler to the substrate 41.
The thickness of the substrate 41 is not particularly limited as long as it can function properly in each step using the composite sheet 3 for forming a protective film. Preferably 20 to 450 μm, more preferably 25 to 400 μm, and particularly preferably 50 to 350 μm.
(3.1.2. adhesive layer)
The adhesive layer 42 included in the adhesive sheet 4 of the composite sheet 3 for forming a protective film according to the present embodiment may be composed of a non-energy ray-curable adhesive or an energy ray-curable adhesive. The non-energy ray-curable adhesive is preferably an adhesive having desired adhesive strength and removability, and examples thereof include acrylic adhesives, rubber adhesives, silicone adhesives, urethane adhesives, polyester adhesives, and polyvinyl ether adhesives. Among them, an acrylic adhesive which has high adhesion to the protective film forming film 1 and can effectively suppress the falling off of the work or the processed product of the work in the dicing step or the like is preferable. Further, an acrylic adhesive is also preferable from the viewpoint of easy control of Ra0 and easy control of pickup suitability of a work with a protective film.
On the other hand, since the energy ray-curable adhesive has a reduced adhesive force due to the irradiation with the energy ray, when it is necessary to separate the work or the processed product of the work from the adhesive sheet 4, the separation can be facilitated by the irradiation with the energy ray.
The energy ray-curable adhesive constituting the adhesive layer 42 may contain a polymer having energy ray-curability as a main component, or a mixture of a polymer having no energy ray-curability and an energy ray-curable monomer and/or oligomer as a main component.
Examples of the energy ray-curable polymer include a (meth) acrylate (copolymer) polymer into which an energy ray-curable group is introduced. Examples of the energy ray-curable monomer and/or oligomer include esters of a polyol and (meth) acrylic acid. The energy ray-curable adhesive may contain an additive such as a photopolymerization initiator or a crosslinking agent in addition to the component having energy ray-curability.
The thickness of the adhesive layer 42 is not particularly limited as long as it can function properly in each step using the composite sheet 3 for forming a protective film. Specifically, the thickness of the adhesive layer is preferably 1 to 50 μm, 2 to 30 μm, 2 to 20 μm, 3 to 10 μm, or 3 to 8 μm.
By setting the upper limit value of the thickness of the adhesive agent layer to the above value, the movement of the protective film forming film in contact with the adhesive agent layer can be controlled, and therefore, the desired surface roughness Ra0 of the protective film is easily obtained, and as a result, the control of Ra1 is also concerned.
As the adhesive constituting the adhesive layer 5 for a jig, an adhesive having a desired adhesive force and removability is preferable, and for example, an acrylic adhesive, a rubber adhesive, a silicone adhesive, a urethane adhesive, a polyester adhesive, a polyvinyl ether adhesive, or the like can be used. Among these, acrylic adhesives are preferred which have high adhesion to a jig such as an annular frame and which can effectively prevent the protective film forming composite sheet 3 from peeling off from the annular frame or the like in a dicing step or the like. Further, a base material as a core material may be inserted in the thickness direction of the adhesive agent layer 5 for a jig.
The thickness of the adhesive layer 5 for a jig is preferably 5 to 200 μm, and particularly preferably 10 to 100 μm from the viewpoint of adhesiveness to a jig such as a ring frame.
(4. method for producing protective film-forming film)
The method for producing the protective film-forming film is not particularly limited. The film can be produced using the above-described composition for forming a protective film, or a composition (coating agent) obtained by diluting the composition for forming a protective film with a solvent. The coating agent can be prepared by mixing the components constituting the composition for forming a protective film by a known method. In the preparation of the coating agent, it is preferable to filter the stirred coating agent through a screen having a mesh size of 160 μm or less. This removes the aggregates of the filler, the curing agent, the resin, and the like, and as a result, Ra0 and Ra1 of the protective film can be easily controlled.
The obtained coating agent is applied to the release surface of the release film using a coater such as a roll coater, a knife coater, an air knife coater, a die coater, a bar coater, a gravure coater, or a curtain coater, and dried, thereby forming a protective film forming film on the first release film. Next, the release surface of the second release film was bonded to the exposed surface of the protective film forming film, and the protective film forming film 1 was sandwiched between two release films to obtain a protective film forming sheet.
When the second release film is attached, it is preferable to perform the attachment while heating to a temperature higher than normal temperature (23 ℃). Before the formation of the protective film, the arrangement state of the fillers on the surface and inside near the surface of the protective film forming film in contact with the first release film, on the surface and inside near the surface of the protective film forming film in contact with the second release film, and the like can be controlled, and Ra0 and Ra1 can also be controlled.
(5. method for producing composite sheet for forming protective film)
The method for producing the composite sheet 3 for forming a protective film is not particularly limited. For example, a first laminate including the protective film forming film 1 and a second laminate including the adhesive sheet 4 as a support sheet are prepared, and then the first laminate and the second laminate are used to laminate the protective film forming film 1 and the adhesive sheet 4.
The first laminate can be produced by the same method as the above protective film-forming sheet. That is, a protective film forming film is formed on the release surface of the first release film, and the release surface of the second release film is bonded to the exposed surface of the protective film forming film.
The first laminate may be half-cut as needed to form the protective film forming film 1 and the second release film into a desired shape, for example, a circular shape. At this time, the unnecessary portions of the protective film forming film 1 and the second release film resulting from the half-cut can be appropriately removed.
On the other hand, in order to produce the second laminate, first, an adhesive composition constituting the adhesive layer 42 or a composition (coating agent) obtained by diluting the adhesive composition with a solvent is prepared. Next, a coating agent is applied to the release surface of the third release film and dried, and the adhesive layer 42 is formed on the third release film. Then, the substrate 41 is bonded to the exposed surface of the adhesive layer 42, and a laminate (second laminate) composed of the adhesive sheet 4 and the third release film is obtained, the adhesive sheet 4 being composed of the substrate 41 and the adhesive layer 42.
Here, when the adhesive layer 42 is formed of an energy ray-curable adhesive, the adhesive layer 42 may be irradiated with an energy ray at this stage to cure the adhesive layer 42, or the adhesive layer 42 may be cured after being laminated with the protective film forming film 1. In addition, in the case where the adhesive layer 42 is cured after being laminated with the protective film forming film 1, the adhesive layer 42 may be cured before the dicing step, or the adhesive layer 42 may be cured after the dicing step.
As the energy ray, ultraviolet rays, electron beams, or the like can be generally used. The dose of the energy ray is determined according to the kind of the energy rayIn contrast, for example, when ultraviolet light is used, it is preferably 50 to 1000mJ/cm in light amount2Particularly preferably 100 to 500mJ/cm2. When an electron beam is used, it is preferably about 10 to 1000 krad.
After the first laminate and the second laminate are obtained in this manner, the second release film of the first laminate is peeled off, and the third release film of the second laminate is simultaneously peeled off, so that the protective film forming film 1 exposed from the first laminate is bonded to the adhesive layer 42 of the adhesive sheet 4 exposed from the second laminate. The adhesive sheet 4 may be cut as needed to form a desired shape, such as a circle having a diameter larger than that of the protective film forming film 1. At this time, the excess portion of the adhesive sheet 4 generated by cutting can be appropriately removed. Further, the protective film forming film and the adhesive layer 42 may be formed in a circular shape or the like having the same diameter.
Thus, a composite sheet 3 for forming a protective film is obtained, which comprises an adhesive sheet 4 having an adhesive layer 42 laminated on a substrate 41, a protective film forming film 1 laminated on the adhesive layer 42 side of the adhesive sheet 4, and a first release film laminated on the protective film forming film 1 on the side opposite to the adhesive sheet 4. After the first release film is peeled off, the adhesive agent layer 5 for a jig may be formed on the exposed protective film forming film 1 or the periphery of the adhesive agent layer 42, as necessary.
(6. method for manufacturing device)
As an example of the method for manufacturing the device using the protective film forming film according to the present embodiment, a method for manufacturing a package in which a chip with a protective film obtained by processing a wafer to which the protective film forming film is attached is disposed on a substrate will be described.
The method for manufacturing the device of the present embodiment includes at least the following steps 1 to 5.
Step 1: a step of attaching the protective film forming film provided in the composite sheet for forming a protective film to the back surface of the wafer;
and a step 2: a step of forming a protective film by forming the attached protective film into a protective film;
step 3: singulating the wafer having the protective film or the protective film forming film on the back surface thereof into individual pieces to obtain a plurality of chips each having the protective film or the protective film forming film;
and step 4: disposing a chip having a protective film or a protective film forming film on a substrate;
step 5: and heating the chip with the protective film and the substrate disposed on the substrate.
As is clear from the above description, the step 2 may be performed before the steps 3 and 4, after the step 3, before the step 4, or after the steps 3 and 4.
In the present embodiment, the method for manufacturing the device preferably includes, after the step 5, a step of performing a covering treatment of the protective film exposed to the chip with the protective film by the sealing member (step 6). By performing step 6, a package in which a plurality of chips including a chip with a protective film are sealed can be obtained as a sealed device.
A method for manufacturing the device having steps 1 to 6 will be described with reference to fig. 4 to 9.
As shown in fig. 4, the protective film forming film 1 of the composite sheet for forming a protective film 3 is attached to the wafer 6 (step 1). At this time, the outer peripheral portion of the protective film forming film 1 may be fixed by the ring frame 7. In the present embodiment, as shown in fig. 4, since the adhesive agent layer 5 for a jig is provided on the outer periphery of the protective film forming film 1, the adhesive agent layer 5 for a jig is attached to the annular frame 7. The wafer 6 is attached to the surface of the protective film forming film 1 opposite to the surface to which the adhesive layer 42 is attached. When the protective film forming film 1 is attached to the wafer 6, the protective film forming film 1 may be heated as necessary to exhibit adhesiveness.
Then, the attached protective film forming film 1 is formed into a protective film (step 2), and a wafer 6 with a protective film is obtained. When the protective film forming film 1 is thermosetting, the protective film forming film 1 may be heated at a prescribed temperature for an appropriate time. When the protective film forming film 1 is energy ray-curable, energy rays may be irradiated from the adhesive sheet 4 side.
The curing of the protective film forming film 1 may be performed after the dicing step, or the protective film forming film may be cured after picking up the chip with the protective film forming film from the adhesive sheet.
Next, the wafer 6 with the protective film is diced by a known method, and as shown in fig. 5, a chip (chip 10 with a protective film) having the protective film 1a is obtained (step 3). Then, as shown in fig. 6, the adhesive sheet 4 is spread in the planar direction as necessary, and the chip 10 with the protective film is picked up from the adhesive sheet 4 by the suction nozzle C.
The picked-up chip 10 with the protective film may be transferred to the next step, or may be temporarily stored and stored on a tray, a tape, or the like, and transferred to the next step after a predetermined time.
The chip 10 with the protective film, which is transferred to the next step, is transferred to the substrate 50 by the suction nozzle C as shown in fig. 7, and the terminal portion on the substrate is separated from the suction nozzle C and is arranged at a position where the connection electrode such as a bump and the terminal portion such as a pad can be connected (step 4). At this time, when the surface roughness of the protective film is too small, a problem may occur in detachment from the suction nozzle, resulting in occurrence of connection failure after the heat treatment. Therefore, as described above, the surface roughness Ra0 of the protective film before heat treatment is preferably 35nm or more. As shown in fig. 8, in the present embodiment, another chip 11 different from the chip 10 with a protective film may be mounted on the substrate 50. Therefore, a plurality of chips are mounted on the substrate.
The chip with the protective film disposed at a predetermined position on the substrate is subjected to a heat treatment (reflow treatment) (step 5). The reflow treatment conditions are preferably, for example, a maximum heating temperature of 180 to 350 ℃ and a reflow treatment time of 2 to 10 minutes.
In the reflow process, the protruding electrodes 6b of the chip 10 with the protective film are melted and electrically and mechanically connected to the terminal portions on the substrate, and the chip 10 with the protective film is mounted on the substrate. Next, in the present embodiment, the plurality of chips mounted on the substrate are covered with the sealing member, whereby the chips 10 with the protective film are sealed (step 6). The plurality of chips may be filled with a sealing member therebetween.
A method of sealing the plurality of chips using the sealing member 30 is not particularly limited. The following methods may be employed: the plurality of chips subjected to reflow processing are placed in a mold, and a sealing resin material having fluidity is injected into the mold, and the sealing resin material is heated and cured to form a sealing resin layer. Further, a method of placing a sheet-like sealing resin so as to cover a plurality of chips and heating and curing the sealing resin to form a sealing resin layer may be employed. Examples of the material of the sealing member include epoxy resin. In addition, since the sealing resin is cured by heating, the "sealing resin" in this specification includes both the sealing resin in contact with the protective film before curing and the sealing resin in contact with the protective film after curing.
After the sealing treatment, a system-in-package 100 (fig. 9) in which the chip 10 with the protective film is covered with a sealing member 30 (sealing resin) is obtained. In this case, since the surface roughness Ra1 of the protective film after heating at 260 ℃ for 5 minutes is within the above range, the surface roughness of the protective film is small even after the reflow process, and the adhesion reliability of the interface between the protective film and the sealing resin is good. Therefore, a system in package with high reliability can be obtained.
As another example of the method for manufacturing a device using a protective film-formed film according to the present embodiment, a method for manufacturing a device in which a chip with a protective film obtained by marking a protective film or a protective film-formed film formed on a chip is disposed on a substrate will be described.
The method for manufacturing the device includes at least steps 1 to 5, and further includes a step (step 7) of laser marking the protective film or the protective film forming film so that the height of the marked portion is greater than 0 μm, as in the method for manufacturing the device described above.
By performing the laser marking, the chip with the protective film forming film or the chip with the protective film can be discriminated from each other during a period from the laser marking to the arrangement before the substrate.
In the laser marking, although the marking can be performed by removing the protective film forming film or the surface of the protective film by laser irradiation, in the present embodiment, it is preferable to perform the marking such that the height of the marked portion (laser irradiated portion) is larger than 0 μm. That is, the marked portion is preferably formed to be convex compared to the unmarked portion. The protective film forming film or the protective film of the marking portion increases in volume with laser irradiation, thereby forming a convex mark.
The height of the labeling part is preferably 0.001 μm or more, 0.005 μm or more, 0.010 μm or more, 0.020 μm or more, or 0.030 μm or more. When the height of the mark portion is larger than 0 μm, the visibility of printing is excellent as compared with 0 μm.
The method for manufacturing the device preferably includes a step (step 6) of performing a covering treatment of the protective film exposed to the chip with the protective film by the sealing member after the step 5, as in the method for manufacturing the device described above. By performing step 6, a package in which a plurality of chips including a chip with a protective film are sealed can be obtained.
In addition, when the mark portion is formed into a concave shape by laser irradiation (when the mark portion is removed), the mark becomes more easily clear than when the mark is formed into a convex shape, and the mark is easily kept clear even after the reflow soldering process. However, when a chip with a protective film, in which the mark portion is recessed, is subjected to a sealing treatment, voids are easily formed in the recessed portion, and as a result, the adhesion reliability between the sealing resin and the protective film is lowered. Therefore, by the height of the mark portion being larger than 0 μm, the adhesion reliability can be improved.
The method for manufacturing the device can be described with reference to fig. 4 to 9, and the description is the same as that of the method for manufacturing the device. In the step of performing laser marking, marking can be performed using a known laser marking apparatus.
(7. modification)
Fig. 3 is a sectional view of a composite sheet for forming a protective film according to another embodiment of the present invention. As shown in fig. 3, the composite sheet 3A for forming a protective film of the present embodiment has the following structure: an adhesive sheet 4 in which an adhesive layer 42 is laminated on one surface of a substrate 41, and a protective film forming film 1 laminated on the adhesive layer 42 side of the adhesive sheet 4. The protective film forming film 1 of the present embodiment is formed such that: almost the same size as the workpiece or slightly larger than the workpiece in plan view, and smaller than the adhesive sheet 4. The adhesive layer 42 in a portion where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.
In addition, a separate adhesive layer for a jig, which is the same as the adhesive layer 5 for a jig of the composite sheet 3 for forming a protective film described above, may be provided in the periphery of the adhesive layer 42 of the adhesive sheet 4 of the composite sheet 3A for forming a protective film.
In order to protect the protective film forming film before use, a release film may be laminated on the surface of the protective film forming composite sheet 3 or 3A on the protective film forming film 1 side.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments and may be modified in various ways within the scope of the present invention.
Examples
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
(test 1)
(production of protective film Forming sheet)
The following components were mixed at the blending ratios (in terms of solid content) shown in table 1, and the mixture was diluted with methyl ethyl ketone to a solid content concentration of 50 mass% to prepare a coating agent. In the preparation of the coating agent, the coating agent was stirred and then passed through a polyester screen having a mesh of 75 μm to carry out filtration, thereby completing the preparation.
(A) Polymer component
(A-1) a (meth) acrylic ester copolymer (weight-average molecular weight: 50 ten thousand, glass transition temperature: -28 ℃ C.) obtained by copolymerizing 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate
(A-2) a (meth) acrylic ester copolymer (weight-average molecular weight: 50 ten thousand, glass transition temperature: 5 ℃ C.) obtained by copolymerizing 3 parts by mass of n-butyl acrylate, 88 parts by mass of methyl acrylate and 9 parts by mass of 2-hydroxyethyl acrylate
(A-3) a (meth) acrylic ester copolymer (weight-average molecular weight: 40 ten thousand, glass transition temperature: 5 ℃ C.) obtained by copolymerizing 3 parts by mass of n-butyl acrylate, 75 parts by mass of methyl acrylate, 7 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate
(B) Curing component (thermosetting component)
(B-1) bisphenol A type epoxy resin (jER 828, epoxy equivalent 184-194 g/eq, manufactured by MITSUBISH CHEMICAL CORPORATION)
(B-2) bisphenol A type epoxy resin (jER 1055, epoxy equivalent 800 to 900g/eq, manufactured by MITSUSH CHEMICAL CORPORATION)
(B-3) Dicyclopentadiene type epoxy resin (EPICLON HP-7200HH, epoxy equivalent 255-260 g/eq, manufactured by chemical engineering of Dajapan インキ)
(B-4) cresol novolak-type epoxy resin (Nippon Kayaku Co., Ltd., manufactured by Ltd., EOCN-104, epoxy equivalent 220g/eq)
(B-5) an epoxy resin having a flexible skeleton (EXA 4850-150, molecular weight 900, epoxy equivalent 450g/eq, manufactured by of chemical engineering, Dajapan インキ)
(C) Curing agent: dicyanodiamide (manufactured by MITSUBISH CHEMICAL CORPORATION, DICY7)
(D) Curing accelerator: 2-phenyl-4, 5-dihydroxymethylimidazole (Curezol 2PHZ, manufactured by SHIKOKU CHEMICALS CORPORATION)
(E) Filling material
(E-1) epoxy-modified spherical silica Filler (manufactured by ADMATECHS CORPORATION, SC2050MA, average particle diameter 0.5 μm)
(E-2) silica Filler (manufactured by Tokuyama Corporation, UF310, average particle diameter 3 μm)
(E-3) amorphous silica Filler (manufactured by TATSUMORI CORPORATION, SV-10, average particle diameter 8 μm)
(F) Silane coupling agent: gamma-glycidyl Ether oxypropyltrimethoxymethylsilane (Shin-Etsu Chemical Co., Ltd., KBM403, methoxy equivalent 12.7mol/g, molecular weight 236.3)
(G) Colorant: carbon black (manufactured by MITSUBISH CHEMICAL CORPORATION, MA600, average particle diameter 20nm)
[ Table 1]
The prepared coating agent was coated on a first release film (manufactured by LINETEC CORPORATION: SP-PET501031 thickness: 50 μm), and dried at 100 ℃ for 2 minutes to form a protective film-forming film having a thickness of 20 μm. Subsequently, a second release film (manufactured by LINETEC CORPORATION: SP-PET381031 thickness: 38 μm) was attached to the protective film forming film, and a protective film forming sheet having release films formed on both surfaces of the protective film forming film was obtained. For the attachment conditions, the temperature was 60 ℃, the pressure 0.6MPa, and the speed 1 m/min.
(production of adhesive sheet)
The following components were mixed at the following blending ratios (in terms of solid content), and the mixture was diluted with methyl ethyl ketone to a solid content concentration of 25 mass% to prepare a coating agent for an adhesive layer. The coating agent contains: 100 parts by mass of an acrylic polymer obtained by copolymerizing 70 parts by mass of 2-ethylhexyl acrylate (2EHA), 20 parts by mass of Methyl Methacrylate (MMA) and 10 parts by mass of 2-hydroxyethyl acrylate (HEA), and 40 parts by mass of trifunctional xylylene diisocyanate (manufactured by MITSUI TAKEDA CHEMICALS, INC., TakenateD 110N).
The prepared coating agent was coated on a third release film (manufactured by LINETEC CORPORATION: SP-PET381031 thickness: 38 μm), and dried at 100 ℃ for 2 minutes to form an adhesive layer having a thickness of 5 μm. Then, a smooth surface of a polypropylene film (manufactured by GUNZE LIMITED, smooth surface on one side/dull surface on the opposite side) having a thickness of 80 μm was attached to the adhesive layer to obtain an adhesive sheet.
(production of composite sheet for Forming protective film)
Using the protective film-forming sheet, adhesive sheet, and adhesive layer for a jig formed on the release film in a shape corresponding to the outer periphery of the protective film-forming film obtained above, composite sheets for protective film formation of examples 1 to 7 and comparative example 1 were obtained, in which the protective film-forming film was formed on the adhesive sheet and the adhesive layer for a jig was formed on the outer periphery of the protective film-forming film.
The obtained composite sheet for forming a protective film was used to perform the following measurement and evaluation.
First, the first release film was peeled off from the composite sheet for forming a protective film of examples 1 to 7 and comparative example 1, and the protective film-forming film of the composite sheet for forming a protective film of examples 1 to 7 and comparative example 1 was attached to the polished surface of a #2000 polished silicon mirror wafer (diameter 150mm, thickness 75 μm) using a film sticking machine ("adwire RAD 2500" manufactured by linec CORPORATION), to obtain a structure as shown in fig. 4.
The silicon mirror wafer with the protective film forming film attached thereto was heated in an oven in an atmosphere at 130 ℃ for 2 hours to form a protective film from the protective film forming film, thereby producing a wafer with a protective film.
(surface roughness of protective film)
The adhesive sheet was peeled off from the wafer with the protective film, and the arithmetic average roughness Ra0(μm) of the surface of the protective film was measured using SV-3000 manufactured by MITSUTOYO corpio CORPORATION. As measurement conditions, according to JIS B0601:2013, the critical value λ c is 0.8mm, and the evaluation length In is 10 mm. The results are shown in table 2.
Subsequently, the adhesive sheet was peeled off from the wafer with the protective film, and the resultant was put into an oven, heated at 260 ℃ for 5 minutes, taken out of the oven, and gradually cooled. After gradually cooling to normal temperature (23 ℃), the arithmetic average roughness Ra1(μm) of the surface of the protective film was measured using SV-3000 manufactured by MITSUTOYO corpio CORPORATION. The measurement conditions were set to a critical value λ c of 0.8mm and an evaluation length In of 10mm In accordance with JIS B0601: 2013. The results are shown in table 2.
(Water contact Angle of protective film surface)
The adhesive sheet was peeled off from the wafer with the protective film, placed in an oven, heated at 260 ℃ for 5 minutes, taken out of the oven, and gradually cooled. After gradually cooling to room temperature (23 ℃), the contact angle obtained with a 2 μ l water droplet was measured using an automatic contact angle measuring instrument ("DSA 100" manufactured by KRUSS CORPORATION) in an environment with a relative humidity of 50% at 23 ℃ with the surface of the protective film as the object of measurement, and this was taken as the water contact angle. The results of measuring the water contact angle are shown in table 2.
(evaluation of adhesion reliability of semiconductor Package)
A dicing die bonding sheet (dicing die bonding sheet) was attached to the wafer with the protective film via a film-like adhesive on the surface opposite to the polished surface on which the protective film was formed, and fixed to the ring frame for dicing. As the film-like adhesive, used were: a film-shaped adhesive having sufficient adhesion reliability, the sufficient adhesion reliability being: when the adhesion reliability test was performed using a structure of a package without a protective film (i.e., a structure of "substrate/film-like adhesive/silicon chip/sealing resin"), the substrate and the silicon chip were not peeled off from each other.
Next, the dicing die-bonded sheet and the silicon wafer with the protective film were cut into a size of 8mm × 8mm using a dicing apparatus ("DFD 651" manufactured by DISCO Corporation), and a semiconductor chip with a protective film was obtained.
Next, the semiconductor chip with the protective film and the film-like adhesive for dicing the die bonding sheet are collectively picked up from the base material using a rubber suction nozzle. As a substrate, a substrate (LN 001E-001pcb (au) AUS303 manufactured by china company) was prepared in which a circuit pattern was formed on a copper foil (thickness 18 μm) of a copper clad laminate (CCL-HL 830 manufactured by MITSUBISHI GAS CHEMICAL co., inc.) and a solder resist (SPR-4000 AUS303 manufactured by TAIYO INK. The semiconductor chip with the protective film was pressure bonded to the substrate through a film-like adhesive at 120 ℃ under 2.45N (250gf) for 0.5 second using a die bonder (BESTEM-D02 manufactured by CANON MACHINERY INC.). After the pressure bonding, the laminate of the substrate and the semiconductor chip with the protective film was subjected to IR reflow under conditions of a maximum heating temperature of 260 ℃ and a heating time of 5 minutes.
Next, these laminated bodies were sealed with a sealing resin ("KE-G125" manufactured by KYOCERA CHEMICAL CORPORATION) at a sealing thickness of 400 μm, and heated at 175 ℃ for 5 hours, thereby curing the sealing resin. Next, the sealed laminate was attached on a dicing tape ("adwide D-510T" manufactured by linec CORPORATION) and cut into a size of 15mm × 15mm using a dicing apparatus ("DFD 651" manufactured by DISCO CORPORATION), to obtain a semiconductor package in which a semiconductor chip with a protective film was sealed with a resin for evaluation of adhesion reliability.
Next, the obtained semiconductor package was allowed to stand at 85 ℃ and a relative humidity of 60% for 168 hours to absorb moisture, and then subjected to IR reflow at a maximum heating temperature of 260 ℃ and a heating time of 5 minutes. Then, the semiconductor package subjected to the IR reflow was inspected for the occurrence of package cracks using a scanning ultrasonic flaw detector (HITACHI KENKI FINE TECH co., Hye-Focus manufactured by ltd.).
The evaluation was performed for each 10 semiconductor packages of the examples and comparative examples, and the adhesion reliability was evaluated by confirming the number of package cracks occurring in 10 packages, and is shown in the column of "adhesion reliability test" in table 2 below. In table 2, for example, the description of "0/10" indicates that 10 semiconductor packages were evaluated, and 0 of the 10 semiconductor packages had a package crack, that is, there was no semiconductor package in which a package crack was observed. The samples with the number of cracks of 5 or more were judged as "poor (F)", the samples with the number of cracks of 2 to 4 were judged as "normal (B)", and the samples with the number of cracks of 0 or 1 were judged as "good (a)".
[ Table 2]
As can be seen from table 2, when the surface roughness Ra1 of the protective film after heating at 260 ℃ for 5 minutes is within the above range, the adhesion reliability of the package is good. Even in the samples having the same Ra1 (examples 1 and 7), the adhesion reliability was confirmed to be excellent even though the sample having a low water contact angle (example 1) was slight.
Further, as is clear from table 2, by using two types of fillers (fillers) having different average particle diameters, the change [ nm ] in Ra before and after heating tends to be suppressed to be small. It was confirmed that the surface roughness Ra1 of the protective film after heating at 260 ℃ for 5 minutes tended to fall within the above range.
In addition, in the process of disposing the semiconductor chip with the protective film on the substrate, the protective films of all the examples and comparative examples were smoothly detached from the rubber suction nozzle. This is presumably due to Ra0 being within the above range.
(test 2)
A semiconductor package in which a semiconductor chip with a protective film was sealed with a resin was prepared in the same manner as in example 1 except that the composite sheet for forming a protective film of example 5 was used and the protective film was subjected to laser marking, and the same adhesion reliability evaluation as in test 1 was performed.
(laser marking)
After the protective film forming film was formed into a protective film, the surface of the protective film was laser-marked by irradiating the protective film with laser light from the adhesive sheet side of the wafer with the composite sheet for forming a protective film using a laser marking apparatus ("CSM 300M" manufactured by EO technologies co. For the irradiation conditions, laser wavelength: 532nm, Draw speed: 20mm/s, Power: 0.11W and 0.14W. In addition, for each chip, 3 lines of "888" (9 words total) are marked, each word having a size of 0.5mm lengthwise by 0.4mm crosswise.
Next, the adhesive sheet was peeled off from the wafer with the protective film after laser marking, and the height of the center portion of the character "8" was measured using a laser microscope ("VK-9700" manufactured by Keyence CORPORATION) in the following procedure. The wafer with the protective film before heating at 260 ℃ was measured.
First, a measurement position (linear shape) on the surface of the protective film is specified so as to straddle unprinted portion/printed portion/unprinted portion. Subsequently, the average height of the 10 μm measurement distance of each unprinted portion on both sides was measured, and the sum of the measured values on both sides was divided by 2 to be referred to as "average height of unprinted portion [ μm ]. Next, the average height of the 10 μm measured distance at the center of the printed portion was measured and is referred to as "average height of printed portion [ μm ]. The height of the printed portion is calculated from the obtained value by the following equation.
Height of printed portion [ μm ] (average height of printed portion) - (average height of unprinted portion)
The above measurement was performed for 4 out of the four corners of the 9 characters, and the average height of the 4 characters was taken as the height of the final printed portion.
The wafer with the protective film after measurement was heated at 260 ℃ for 5 minutes and diced in the same manner as in test 1, to obtain semiconductor chips with a protective film. Using the obtained semiconductor chip with a protective film, a semiconductor package in which the semiconductor chip with a protective film was sealed with a resin was obtained in the same manner as in test 1. The obtained semiconductor package was subjected to adhesion reliability evaluation in the same manner as in test 1.
When the power was 0.11W at the time of laser marking, the height of the printed portion was 0.019 μm, printing could be recognized, and a result of "0/10" was obtained in the adhesion reliability test (judged as a).
When the power was 0.14W at the time of laser marking, the height of the printed portion was 0.038 μm, printing could be recognized, and a result of "0/10" was obtained in the adhesion reliability test (judged as a).
It is presumed that even when laser marking is performed, since the height of the marked portion is larger than 0 μm, printing can be recognized without adversely affecting the adhesion reliability.
Further, when the wafer with the protective film after laser marking is heated at 260 ℃, the printed characters visually recognized tend to be unclear compared with those before heating, but in the case of performing the sealing treatment, the marked portion is covered with the sealing resin, so that no significant problem is caused.
Industrial applicability
The protective film forming film and the protective film forming composite sheet of the present invention are suitably used for manufacturing a package in which a chip with a protective film is packaged.
Claims (11)
1. A protective film-forming film for forming a protective film, wherein the protective film has a surface roughness Ra1 of 200nm or less after heating at 260 ℃ for 5 minutes.
2. The protective film forming film according to claim 1, wherein a water contact angle of the protective film is 107 ° or less.
3. The protective film forming film according to claim 1 or 2, wherein a surface roughness Ra0 of the protective film before heating at 260 ℃ for 5 minutes is 35nm or more.
4. The protective film forming film according to any one of claims 1 to 3, wherein the protective film is a heat-cured product or an energy ray-cured product.
5. The protective film forming film according to any one of claims 1 to 4, wherein the protective film contains a filler.
6. The protective film forming film according to claim 5, wherein the filler material is composed of two or more filler materials having different average particle diameters.
7. A composite sheet for forming a protective film, which comprises the protective film forming film according to any one of claims 1 to 6 laminated on a support sheet.
8. A method of manufacturing a device, comprising:
a step of attaching the protective film-forming film according to any one of claims 1 to 6 or the protective film-forming film provided in the composite sheet for forming a protective film according to claim 7 to the back surface of a workpiece;
a step of forming a protective film by forming the attached protective film into a protective film;
singulating the workpiece having the protective film or the protective film forming film on the back surface thereof into individual pieces to obtain a plurality of processed products of the workpiece having the protective film or the protective film forming film;
disposing the work piece with the protective film or the protective film forming film on a substrate; and
and heating the work with the protective film disposed on the substrate and the substrate.
9. A method of manufacturing a device, comprising:
a step of attaching the protective film-forming film according to any one of claims 1 to 6 or the protective film-forming film provided in the composite sheet for forming a protective film according to claim 7 to the back surface of a workpiece;
a step of forming a protective film by forming the attached protective film into a protective film;
a step of laser marking the protective film or the protective film forming film so that the height of the marked part is greater than 0 [ mu ] m;
singulating the workpiece having the protective film or the protective film forming film on the back surface thereof into individual pieces to obtain a plurality of processed products of the workpiece having the protective film or the protective film forming film;
disposing the work piece with the protective film or the protective film forming film on a substrate; and
and heating the work with the protective film disposed on the substrate and the substrate.
10. The method for manufacturing the device according to claim 8 or 9, wherein a step of covering the protective film exposed to the work with the protective film with the sealing member is provided after the step of heating the work with the protective film arranged on the substrate and the substrate.
11. The method of manufacturing the device according to any one of claims 8 to 10, wherein the workpiece is a wafer, and the work of the workpiece is a chip.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020016594A JP7457513B2 (en) | 2020-02-03 | 2020-02-03 | PRODUCTION METHOD OF PROTECTIVE FILM-FORMING FILM, COMPOSITE SHEET FOR PROTECTIVE FILM-FORMING, AND APPARATUS |
| JP2020-016594 | 2020-02-03 |
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|---|---|
| CN113206039A true CN113206039A (en) | 2021-08-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110047614.5A Pending CN113206039A (en) | 2020-02-03 | 2021-01-14 | Protective film forming film, composite sheet for forming protective film, and method for manufacturing device |
Country Status (4)
| Country | Link |
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| JP (1) | JP7457513B2 (en) |
| KR (1) | KR20210098848A (en) |
| CN (1) | CN113206039A (en) |
| TW (1) | TW202130773A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4321897B2 (en) | 1999-02-25 | 2009-08-26 | 株式会社小松製作所 | Semiconductor die |
| JP2003115424A (en) | 2001-10-03 | 2003-04-18 | Nec Corp | Semiconductor device, its identifying method, and semiconductor device manufacturing device |
| JP5544872B2 (en) | 2009-12-25 | 2014-07-09 | 富士通セミコンダクター株式会社 | Semiconductor device and manufacturing method thereof |
| JP5249290B2 (en) | 2010-07-20 | 2013-07-31 | 日東電工株式会社 | Flip chip type semiconductor back film, dicing tape integrated semiconductor back film, semiconductor device manufacturing method, and flip chip type semiconductor device |
| JP2016139642A (en) | 2015-01-26 | 2016-08-04 | 株式会社東芝 | Semiconductor device |
| SG11201704075PA (en) | 2015-03-30 | 2017-10-30 | Lintec Corp | Sheet for forming resin film and composite sheet for forming resin film |
| JP6078578B2 (en) | 2015-04-22 | 2017-02-08 | 日東電工株式会社 | Flip chip type film for semiconductor back surface and use thereof |
| TWI778960B (en) | 2016-04-28 | 2022-10-01 | 日商琳得科股份有限公司 | Film for forming protective film, composite sheet for forming protective film, and method of manufacturing semiconductor chip having protective film |
| CN110392924B (en) | 2017-02-21 | 2022-11-15 | 三菱电机株式会社 | Semiconductor device with a plurality of semiconductor chips |
| TWI791650B (en) | 2017-10-27 | 2023-02-11 | 日商琳得科股份有限公司 | Film for forming protective coating, composite sheet for forming protective coating, and method of manufacturing semiconductor chip |
| WO2019230682A1 (en) | 2018-05-31 | 2019-12-05 | コニカミノルタ株式会社 | Electronic device and method for producing same |
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2020
- 2020-02-03 JP JP2020016594A patent/JP7457513B2/en active Active
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- 2021-01-14 CN CN202110047614.5A patent/CN113206039A/en active Pending
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| JP2021125514A (en) | 2021-08-30 |
| JP7457513B2 (en) | 2024-03-28 |
| TW202130773A (en) | 2021-08-16 |
| KR20210098848A (en) | 2021-08-11 |
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